Curable composition, coating composition, paint, antifouling paint, cured product thereof and method of rendering base material antifouling

ABSTRACT

A curable composition comprising (A) an organopolysiloxane having functional groups capable of condensation reaction at both molecular terminals thereof and (B-1) a hydrophobic silica and a hydrophilic silica. A curable composition comprising (A) an organopolysiloxane having functional groups capable of condensation reaction at both molecular terminals thereof and (B-2) a hydrophobic silica, wherein the hydrophobic silica (B-2) is thermally treated together with the organopolysiloxane (A).

FIELD OF THE INVENTION

The present invention relates to a curable composition, a coatingcomposition, a paint, an antifouling paint, cured products thereof and amethod of rendering a base material antifouling. More particularly, thepresent invention is concerned with a curable composition which isexcellent in, for example, sprayability and enables forming a thickcoating film by one coating. The curable composition enables shorteningthe operating period for coating, and a coating film of uniformthickness can be obtained by the application thereof. The obtainedcoating film is excellent in film strength, film hardness, rubberproperties, etc. and, for example, exerts excellent antifoulingcapability for a prolonged period of time. Further, the curablecomposition ensures excellent storage stability before applicationthereof. Thus, the present invention is further concerned with a coatingcomposition, a paint, an antifouling paint, cured products thereof and amethod of rendering antifouling a base material such as an underwaterstructure or a ship shell plate.

BACKGROUND OF THE INVENTION

In the production of curable silicone rubber compositions, it is commonpractice to load the composition, irrespective of being the one-packagetype or the two-package type, with a hydrophilic silica or a hydrophobicsilica having its surface treated with, for example,hexamethyldisilazane in order to ensure satisfactory exertion ofproperties such as surface smoothness and rubber strength after curing.

However, the affinity of the hydrophilic silica with silicone oil ispoor, so that aggregates of fillers such as the silica occur in thecured silicone rubber compositions. Rubbers with excellent propertiescannot be obtained by curing of these curable silicone rubbercompositions. On the other hand, the affinity of the hydrophobic silicawith silicone oil is so high that aggregation in the compositions isscarce. Silica is relatively satisfactorily dispersed therein, and thethixotropy thereof is relatively satisfactory. Thus, it is expected thatthe compositions, even when applied to, for example, a vertical surface,can form a thick coating film by one-time application thereof. However,these compositions have high viscosity and accordingly exhibit poorsprayability. Further, these compositions, when diluted with a solvent,rapidly lose thixotropy to thereby cause such problems that the coatingfilm suffers from sagging and that the smoothness of the coating film isdeteriorated.

For example, first, Japanese Patent Laid-open Publication No.10(1998)-316933 discloses a paint composition comprising, as principalcomponents, a room temperature curable silicone rubber having a numberaverage molecular weight of 20,000 to 100,000 (a), a room temperaturecurable silicone rubber having a number average molecular weight of 500to 20,000 (b) and a silicone oil (c), and also discloses a paintcomposition further loaded with a hydrophobic fumed silica (d). Thispaint composition characterized by loading two types of silicone rubbersdiffering in molecular weight with a hydrophobic fumed silica, althoughcan form a thick coating film by one-time application, poses thefollowing problems. That is, the storage stability of the paintcomposition is poor. The paint composition, during the preparation andstorage, may be gelatinized probably due to the secondary aggregation ofsilica, so that the sprayability thereof is poor at the time ofapplication. At the formation of coating film, the surface of thecoating film becomes nonuniform (film thickness and tone are nonuniform,and coating marks are observable), with the result that a coating filmwhich is excellent in film thickness, rubber strength, etc. cannot beobtained.

Apart from the above, for example, underwater structures and fishingnets are used in water, especially sea water, for a prolonged period oftime. Thus, when a multiplicity of sea lives, such as hydrozoans,Bugula, sea lettuces, green lavers, serpulas and oysters, adhere toparts in contact with sea water and breed there, there is the danger ofdeterioration of the inherent functions of the underwater structures andfishing nets. In particular, underwater structures, such as supply waterinlets and waste water outlets, for thermal power plants and nuclearpower plants are constructed and fixed at given positions in the sea,and culture nets and stationary nets are placed in the sea for aprolonged period of time. Therefore, they are likely to suffer fromerosion due to the sea lives and to suffer from conspicuous breeding ofthe sea lives, so that frequent replacement and cleaning thereof areinevitable. These cause a serious economic loss.

In order to resolve the above problems, it is common practice to applyan antifouling paint to the surface of underwater structures, fishingnets, sea water utilizing apparatus, etc. so as to prevent the stickingof sea lives.

For example, secondly, Japanese Patent Publication No. 63(1988)-2995discloses a nonpoisonous antifouling paint composition obtained bymixing together a silicone rubber curable by chemical reaction, apetrolatum or liquid paraffin mixture and a low-viscosity silicone oil.In this reference, it is described that application of the paintcomposition to parts of undersea structure brought into contact with seawater enables preventing sticking and growth of sea lives for aprolonged period of time. However, with the use of this nonpoisonousantifouling paint composition, it is difficult to obtain a satisfactoryfilm thickness by one-time application. Further, there is the problemthat the obtained coating film is poor in strength and hardness and ishence likely to suffer from scratching.

Moreover, thirdly, in Japanese Patent No. 2,522,854 granted on theinvention formerly proposed by the present applicants, there isdisclosed a curable organopolysiloxane composition, together with aproduct curing thereof, comprising as principal components (A) anorganopolysiloxane having its both molecular chain terminals blocked bya silanol group or a hydrolyzable group, (B) an organosilane representedby the formula: R¹ _(a)SiX_(4−a) (wherein R¹ represents an unsubstitutedor substituted monovalent hydrocarbon group having 1 to 8 carbon atoms;X represents a hydrolyzable group; and a is 0 or 1), or a partialhydrolyzate of the organosilane, and (C) an organopolysiloxanecontaining, per molecule, at least one group of the formula: ≡SiR²OSiR³_(b)Y_(3−b) (wherein R² represents an unsubstituted or substituteddivalent hydrocarbon group or a divalent hydrocarbon group containing anether bond; R³ represents an unsubstituted or substituted monovalenthydrocarbon group; Y represents a hydrolyzable group; and b is 0, 1 or2, provided that, when R² represents a divalent hydrocarbon groupcontaining an ether bond, an organopolysiloxane wherein two or moretrimethylsiloxy groups are bonded to the Si atom to which a carbon atomof the hydrocarbon group is directly bonded is excluded). Further, it isdescribed in the patent that the organopolysiloxane composition can beloaded with, as fillers, not only particulate silica, fumed silica,precipitated silica and the like but also those whose surface has beenrendered hydrophobic with the use of, for example, a silane. Stillfurther, it is described in the patent that the cured is free from thedanger of environmental pollution and that the antifouling effectpersists for a prolonged period of time. However, with respect to thecurable organopolysiloxane composition described in the patent, not onlyis there room for improvement in the thickness increase, strength,hardness, etc. of the coating film but also the problem of poorresistance to scratching is posed.

Moreover, the antifouling paint composition described in the firstreference Japanese Patent Laid-open Publication No. 10(1998)-316933,although can form a thick coating film by one-time application asaforementioned, has poor storage stability in the use as a paint,exhibits poor sprayability at the time of coating and causes the coatingfilm to have a nonuniform surface (film thickness and tone arenonuniform, and coating marks are observable) at the time of coatingfilm formation. Thus, desirable coating films cannot be formedtherefrom, and, especially in the use as an antifouling coating film,the problem that the coating film is poor in long-term antifoulingproperties is posed.

OBJECT OF THE INVENTION

The present invention has been made with a view toward solving the aboveproblems of the prior art. It is an object of the present invention toprovide a curable composition which is excellent in properties such aslow viscosity and high thixotropy with a good balance thereof and whichcan form a thick coating film by one-time application, the coating filmupon curing being excellent in properties such as rubber strength andsurface smoothness with a good balance thereof.

It is another object of the present invention to provide a curablecomposition (specifically a coating composition, a curable paintcomposition or an antifouling paint composition) which, when used as acoating material, especially a paint, exhibits excellent sprayabilityand enables forming a thick coating film by one-time application tothereby enable shortening the operating period for coating. A desirablecoating film which is excellent in the uniformity of coating filmsurface can be obtained by the application thereof, which coating filmis also excellent in film strength and film hardness and, when used forantifouling purposes, exerts excellent antifouling capability for aprolonged period of time. Further, the curable composition ensuresexcellent storage stability before application thereof.

It is a further object of the present invention to provide, by the useof the curable composition as a coating material, especially paint, asmentioned above, an electrical part, a building material, a craftworkobject, an apparel industry supply and a medical supply which areexcellent in properties such as film strength, film hardness and surfacesmoothness. It is still a further object of the present invention toprovide, by the use of the curable composition as an antifouling paint,an antifouling coating film which exhibits excellent antifoulingcapability for a prolonged period of time or, for example, an underwaterstructure or a ship shell plate covered with the coating film.

It is an even further object of the present invention to provide aprocess for producing a curable composition, a coating composition or acurable (antifouling) paint composition, from which a thick coating filmof the above properties can be obtained preferably by one-timeapplication.

It is yet an even further object of the present invention to provide amethod of forming a coating film on the surface of, for example, anelectrical part or a method of rendering antifouling the surface of abase material such as a ship shell plate, an underwater structure or afishing net, wherein the above coating film with excellent propertiescan be efficiently formed on the surface of various base materials suchas an underwater structure in a manner ensuring worker's safety and freefrom the danger of environmental pollution.

SUMMARY OF THE INVENTION

The first curable composition of the present invention comprises:

(A) an organopolysiloxane having functional groups capable ofcondensation reaction at both molecular terminals thereof, and

(B-1) a hydrophobic silica and a hydrophilic silica.

The second curable composition of the present invention comprises:

(A) an organopolysiloxane having functional groups capable ofcondensation reaction at both molecular terminals thereof, and

(B-2) a hydrophobic silica,

wherein the hydrophobic silica (B-2) is thermally treated together withthe organopolysiloxane (A).

The hydrophobic silica (B-2) may be thermally treated together with partof the organopolysiloxane (A) or all of the organopolysiloxane (A).

In the present invention, it is preferred that the organopolysiloxane(A) be represented by the formula:

wherein W represents a hydroxyl group or a hydrolyzable group; each ofR¹ and R independently represents an unsubstituted or substitutedmonovalent hydrocarbon group having 1 to 12 carbon atoms, provided thatthe hydrocarbon groups R¹ as well as the hydrocarbon groups R may beidentical with or different from each other; n is an integer of 5 orgreater; and a is 0, 1 or 2.

In the present invention, when, in the formula [α], W represents ahydroxyl group and a is 2, it is preferred that, in addition to thecomponent (A) and component (B-1) or (B-2), the curable compositioncontains:

(C) an organosilane represented by the formula:

R¹ _(b)SiX_(4−b)  [I]

 wherein R¹ represents an unsubstituted or substituted monovalenthydrocarbon group having 1 to 8 carbon atoms; X represents ahydrolyzable group; and b is 0 or 1, or

a partial hydrolyzate of the organosilane.

In the first curable composition of the present invention, it ispreferred that, among the components (B-1), at least the hydrophilicsilica, especially both the hydrophilic silica and the hydrophobicsilica, be thermally treated at 100° C. or higher together with theorganopolysiloxane (A).

In the second curable composition of the present invention, it ispreferred that the hydrophobic silica be thermally treated at 100° C. orhigher together with the organopolysiloxane (A).

In the present invention, preferably, the curable composition containsthe component (B-1) or (B-2) in an amount of 1 to 100 parts by weightper 100 parts by weight of the organopolysiloxane (A).

Further, the curable composition of the present invention preferablycontains the component (C) in an amount of 1 to 20 parts by weight per100 parts by weight of the organopolysiloxane (A).

In the first curable composition of the present invention, it ispreferred that the hydrophobic silica (a) and the hydrophilic silica (b)be contained at a weight ratio ((a)/(b)) of 1/99 to 99/1.

In the present invention, further, a silicone oil (D) is preferablycontained in a total amount of 0.1 to 200 parts by weight per 100 partsby weight of the organopolysiloxane (A).

In the present invention, further, a catalyst, an antifouling agentand/or a colorant is preferably contained in the curable composition.

The process for producing the first curable composition according to thepresent invention comprises heating the organopolysiloxane (A) and atleast the hydrophilic silica among the hydrophobic silica andhydrophilic silica (B-1) at 100° C. or higher.

The coating composition of the present invention comprises any of theabove curable compositions.

In the present invention, the coating composition is preferably used asa paint or an antifouling paint.

The cured product of the present invention is obtained by curing any ofthe above curable compositions.

The coating film or antifouling coating film of the present invention isobtained by application and curing any of the above curable compositions(especially, antifouling paint).

The coated base material of the present invention comprises a basematerial having its surface covered with a coating film obtained bycuring any of the above curable compositions (especially, coatingcompositions). The base material is, for example, an electrical part, anelectronic part, a building material, a craftwork object, an apparelindustry supply or a medical supply.

The method of forming a coating film on a surface of a base materialaccording to the present invention comprises coating or impregnating asurface of a base material, such as an electrical part, with a coatingcomposition comprising any of the above curable compositions, andsubsequently curing the coating composition to thereby form a coatingfilm.

The antifouling base material of the present invention comprises a basematerial brought into contact with sea water or fresh water, having itssurface covered with a coating film obtained by curing any of the abovecurable compositions (especially, antifouling paints). The base materialis preferably any of underwater structures, ship shell plates, fishingnets and fishing gears.

The method of rendering a base material antifouling according to thepresent invention comprises coating or impregnating a surface of a basematerial, such as an underwater structure, with an antifouling paintcomprising any of the above curable compositions, and subsequentlycuring the antifouling paint to thereby form an antifouling coatingfilm.

By virtue of the present invention, there is provided a curablecomposition which is excellent in properties such as low viscosity andhigh thixotropy with a good balance thereof and which can form a thickcoating film by one-time application, the coating film upon curing beingexcellent in properties such as rubber strength and surface smoothnesswith a good balance thereof.

Further, by virtue of the present invention, there is provided a curablecomposition which, especially when used as a coating composition or apaint, exhibits excellent sprayability and enables forming a thickcoating film by one-time application to thereby enable shortening theoperating period for coating. A coating film of uniform thickness can beobtained by the application thereof, which coating film is alsoexcellent in film strength and film hardness and, when used forantifouling purposes, exerts excellent antifouling capability for aprolonged period of time. Furthermore, the curable composition ensuresexcellent storage stability before application thereof.

The above curable composition is suitable for use as a coatingcomposition, especially a curable paint composition or an antifoulingpaint composition.

The cured product, especially coating composition cured product, of thepresent invention is excellent in rubber properties such as surfacegloss, rubber hardness and tensile strength with a good balance thereof.In particular, the (antifouling) coating film and the underwaterstructure or ship shell plate wherein the base material surface iscovered with the antifouling coating film exhibit excellent antifoulingcapability for a prolonged period of time.

The process for producing a curable composition according to the presentinvention enables forming a coating of desired thickness on a surfaceof, for example, a vertically erected base material by one-timeapplication. The process enables producing a curable composition such asa coating material or a paint, especially an antifouling paint, ensuringhigh coating efficiency.

The method of rendering antifouling the surface of a base materialaccording to the present invention enables efficiently forming the abovedesired coating film with excellent properties on the surface of variousbase materials such as an underwater structure in a manner ensuringworker's safety and free from the danger of environmental pollution.

DETAILED DESCRIPTION OF THE INVENTION

The curable composition, coating composition, paint, antifouling paint,cured product thereof and method of rendering a base materialantifouling according to the present invention will be described indetail below.

Curable Composition

The first curable composition of the present invention (also referred toas “the first invention”) comprises:

(A) an organopolysiloxane having functional groups capable ofcondensation reaction at both molecular terminals thereof (terminals ofchain molecule or main chain of molecule), and

(B-1) a hydrophobic silica and a hydrophilic silica.

The second curable composition of the present invention (also referredto as “the second invention”) comprises:

(A) an organopolysiloxane having functional groups capable ofcondensation reaction at both molecular terminals thereof (terminals ofchain molecule or main chain of molecule), and

(B-2) a hydrophobic silica,

wherein the hydrophobic silica (B-2) is thermally treated together withthe organopolysiloxane (A).

The hydrophobic silica (B-2) may be thermally treated together with partof the organopolysiloxane (A) or all of the organopolysiloxane (A).

First, the organopolysiloxane (A) will be described.

Organopolysiloxane (A)

The polymer, preferably liquid polymer, constituting a main component oforganosilicone as described in Japanese Patent No. 2,522,854 is used asthe organopolysiloxane (A). This organopolysiloxane (A) is preferablyrepresented by the formula:

wherein W is a functional group capable of condensation reaction andrepresents a hydroxyl group (—OH) or a hydrolyzable group; each of R¹and R independently represents an unsubstituted or substitutedmonovalent hydrocarbon group having 1 to 12 carbon atoms, provided thatthe hydrocarbon groups R¹ as well as the hydrocarbon groups R may beidentical with or different from each other; n is an integer of 5 orgreater; and a is 0, 1 or 2.

In this formula [α], when a =0 or 1, it is preferred that W represent ahydrolyzable group. On the other hand, when a=2, it is preferred that Wrepresent a hydroxyl group (—OH).

In the present invention, when, in the formula [α], W represents ahydroxyl group and a is 2, it is preferred that, in addition to thecomponent (A) and component (B-1) or (B-2), the curable compositioncontains (C) an organosilane represented by the formula:

R¹ _(b)SiX_(4−b)  [I]

wherein R¹ represents an unsubstituted or substituted monovalenthydrocarbon group having 1 to 8 carbon atoms; X represents ahydrolyzable group; and b is 0 or 1, or

a partial hydrolyzate of the organosilane.

The organopolysiloxane (A) represented by the formula [α] will now bedescribed in greater detail.

When W of the formula [α] represents a hydrolyzable group, it can be,for example, any of an alkoxy group, an acyloxy group, an alkenyloxygroup, an iminoxy group, an amino group, an amido group and an aminoxygroup. Of these, an alkoxy group is preferred.

The alkoxy group is preferably one wherein the total number of carbonatoms is 1 to 10. At least one oxygen atom may be present between carbonatoms thereof. For example, the alkoxy group can be any of methoxy,ethoxy, propoxy, butoxy, methoxyethoxy and ethoxyethoxy.

The acyloxy group is preferably an aliphatic or aromatic grouprepresented by the formula RCOO— (wherein R represents an alkyl grouphaving 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbonatoms). For example, the acyloxy group can be any of acetoxy,propionoxy, butyloxy and benzoyloxy.

The alkenyloxy group is preferably one having about 3 to 10 carbonatoms. It can be, for example, any of isopropenyloxy, isobutenyloxy and1-ethyl-2-methylvinyloxy.

The iminoxy group (RR′C═N—O—, also known as an oxyimino group or aketoxime group) is preferably one having about 3 to 10 carbon atoms. Itcan be, for example, any of dimethyl ketoxime, methyl ethyl ketoxime,diethyl ketoxime, cyclopentanoxime and cyclohexanoxime groups.

The amino group is preferably one having 1 to 10 carbon atoms. It canbe, for example, any of N-methylamino, N-ethylamino, N-propylamino,N-butylamino, N,N-dimethylamino, N,N-diethylamino and cyclohexylaminogroups.

The amido group is preferably one wherein the total number of carbonatoms is 2 to 10. It can be, for example, any of N-methylacetamido,N-ethylacetamido and N-methylbenzamido groups.

The aminoxy group is preferably one wherein the total number of carbonatoms is 2 to 10. It can be, for example, either of N,N-dimethylaminoxyand N,N-diethylaminoxy groups.

Each of R¹ and R independently represents an unsubstituted orsubstituted monovalent hydrocarbon group having 1 to 12, preferably 1 to10, still preferably 1 to 8, carbon atoms. Such monovalent hydrocarbongroup can be, for example, any of alkyl, alkenyl, aryl, cycloalkyl andaralkyl groups.

The alkyl group can be any of linear, branched and alicyclic alkylgroups. It is preferred that the alkyl group be a linear or branchedalkyl group having about 1 to 10, especially 1 to 8, carbon atoms or acycloalkyl group having 3 to 6 carbon atoms.

This linear or branched alkyl group can be, for example, any of methyl,ethyl, propyl, butyl, 2-ethylbutyl and octyl. Of these, methyl isespecially preferred.

The alkenyl group is preferably one having about 2 to 10, stillpreferably 2 to 8, carbon atoms. It can be, for example, any of vinyl,hexenyl and allyl.

The aryl group is preferably one having about 6 to 15, still preferably6 to 12, carbon atoms. It can be, for example, any of phenyl, tolyl,xylyl, naphthyl and diphenyl. Of these, phenyl is especially preferred.

The cycloalkyl group is preferably one having 3 to 8, still preferably 3to 6, carbon atoms. It can be, for example, cyclohexyl or cyclopentyl.

The aralkyl group is preferably one wherein the total number of carbonatoms is about 7 to 10, still preferably 7 to 8, carbon atoms. It canbe, for example, benzyl or 2-phenylethyl.

Some or all of the hydrogen atoms, bonded to the carbon atoms, of thesegroups R¹ may be replaced by, for example, a halogen atom such as F, Cl,Br or I or a cyano group. As such a halogenated alkyl group, there canbe mentioned, for example, chloromethyl, 3,3,3-trifluoropropyl or2-cyanoethyl.

Among the groups R, unsubstituted monovalent hydrocarbon groups arepreferred. Methyl and phenyl are especially preferred.

When a plurality of groups R¹ and a plurality of groups R are present inthe organopolysiloxane (A) represented by the formula [α], theseplurality of groups R¹, plurality of groups R as well as groups R¹ and Rmay be identical with or different from each other.

Although the viscosity at 25° C. of the organopolysiloxane (A) is varieddepending on the use of the employed curable composition and cannot beindiscriminately specified, it is generally preferred from the viewpointof the applicability of the obtained composition and the antisaggingproperties of a solvent dilution of the obtained composition that theviscosity be in the range of 25 to 1,500,000 cS, especially 25 to500,000 cS, still especially 500 to 200,000 cS, and yet still especially1,000 to 100,000 cS.

Hydrophobic Silica and Hydrophilic Silica (B)

There are various silicas, for example, hydrophilic silicas (silica withan untreated surface), such as wet process silica (silica hydrate) anddry process silica (fumed silica or anhydrous silica); and hydrophobicsilicas with a treated surface, such as hydrophobic wet silica andhydrophobic fumed silica.

The first curable composition of the present invention contains amixture of a hydrophobic silica and a hydrophilic silica as silicacomponent (B-1). In the second curable composition of the presentinvention, a hydrophobic silica thermally treated together with theorganopolysiloxane (A) as aforementioned is used as silica component(B-2). Thus, the coating material (coating composition) or paint,especially antifouling paint, from the obtained curable composition ishighly stable during the preparation, safekeeping and storage, exhibitssatisfactory thixotropy and can form a thick coating film by one-timeapplication. The obtained coating film is excellent in rubber propertiessuch as hardness, tensile strength and elongation with a good balancethereof, and, when used as an antifouling coating film, is superior inantifouling properties.

In the first curable composition of the present invention, silicas withthe below mentioned properties can be used directly without anytreatment as the silica component. In a preferred mode, however, atleast the hydrophilic silica among the silica components (B-1), namelythe hydrophobic silica and hydrophilic silica, should be thermallytreated together with part or all of the organopolysiloxane (A), asdescribed in detail below. It is still preferred that both thehydrophilic silica and the hydrophobic silica be thermally treatedtogether with part or all of the organopolysiloxane (A).

The silica component (B-2) used in the second curable composition of thepresent invention, as described in detail below, is the hydrophobicsilica thermally treated together with part or all of theorganopolysiloxane (A).

As aforementioned, there are various silicas, for example, hydrophilicsilicas such as wet process silica and dry process silica as well ashydrophobic silica. Of these silicas, the wet process silica as a memberof the hydrophilic silicas generally exhibits an adsorbed water content(also referred to simply as “water content”) of about 4 to 8%, a bulkdensity of 200 to 300 g/lit., a primary particle diameter of 10 to 30mμ, a specific surface area (in terms of BET) of at least 10 m²/g,preferably about 50 to 800 m²/g, and still preferably 100 to 300 m²/g.

The water content of the dry process silica (fumed silica) is generally1.5% or less. The dry process silica, although its initial watercontent, for example, immediately after the production thereof, is aslow as, for example, 0.3% or less, slowly absorbs moisture while beingallowed to stand still with the result that the water content isincreased to, for example, about 0.5 to 1.0% after the passage ofseveral months after the production thereof. The bulk density of the dryprocess silica, although varied depending on the type thereof and cannotbe indiscriminately specified, is, for example, in the range of 50 to100 g/lit. The primary particle diameter thereof is in the range of 8 to20 mμ, and the specific surface area (in terms of BET) can be at least10 m²/g, preferably about 100 to 400 m²/g, and still preferably 180 to300 m²/g.

The hydrophobic silica is obtained by treating the surface of the abovehydrophilic silica with an organosilicon compound such asmethyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane,hexamethylcyclotrisiloxane or octamethylcyclotetrasiloxane. Inparticular, the hydrophobic fumed silica obtained by treating thesurface of the dry process silica with an organosilicon compound ispreferred. With respect to the hydrophobic fumed silica, the moistureabsorption while the silica is allowed to stand still is slight, and thewater content is generally 0.3% or less, often in the range of 0.1 to0.2%. The specific surface area thereof can be at least 10 m²/g,preferably 100 to 300 m²/g, and still preferably 120 to 230 m²/g. Theprimary particle diameter thereof is in the range of 5 to 50 mμ, and thebulk density is in the range of 50 to 100 g/lit.

With respect to the hydrophobic fumed silica thermally treated togetherwith the component (A) (thermally treated hydrophobic fumed silica), thewater adsorbed on the surface of the hydrophobic silica is reduced orremoved physically, and the water content is generally 0.2% or less,preferably 0.1% or less, and still preferably in the range of 0.05 to0.1%. The bulk density and other properties are similar to those of theabove hydrophobic silica.

It is preferred that the above silica component (B-1) or (B-2) becontained in the curable composition of the present invention generallyin an amount of 1 to 100 parts by weight, especially 2 to 50 parts byweight, and still especially 5 to 30 parts by weight, per 100 parts byweight of the component (A).

Loading the curable composition with the above amount of silicacomponent (B-1) or (B-2) preferably enables producing a coating film ofhigh strength and high hardness and enables providing a compositionwhich exhibits such good thixotropy and has such an appropriateviscosity that desirable coating, especially spray coating, can beeffected. For example, a thick coating film can preferably be formed onthe surface of even a vertically erected base material or the like byone-time application.

In the first curable composition of the present invention, it ispreferred that the hydrophobic silica (a), such as the above hydrophobicfumed silica, and the hydrophilic silica (b), such as silica withuntreated surface, be used as the silica component (B-1) at a weightratio ((a)/(b)) of 1/99 to 99/1, especially 20/80 to 80/20, and stillespecially 30/70 to 70/30.

When the hydrophobic fumed silica (a) is employed in combination withthe hydrophilic silica (b) at the above weight ratio, the obtainedcurable composition is excellent in the paint stability during thepreparation, safekeeping and storage, and has satisfactory thixotropy.The coating film obtained by curing the composition tends to have highstrength and high hardness.

Organosilane or Partial Hydrolyzate Thereof (C)

In the present invention, when the component (A) is represented by theformula [α], and when, in the formula [α], W represents a hydroxyl groupand a is 2, it is preferred that, in addition to the component (A) andcomponent (B-1) or (B-2), the curable composition contain (C) anorganosilane represented by the formula: R¹ _(b)SiX_(4−b) [I] (whereinR¹ represents an unsubstituted or substituted monovalent hydrocarbongroup, like that represented by R and R¹ of the formula [α], having 1 to8 carbon atoms; X represents a hydrolyzable group, like that representedby W of the formula [α]; and b is 0 or 1), or a partial hydrolyzate ofthe organosilane.

Specifically, in the present invention, when an organopolysiloxanehaving hydroxyl groups (—OH) at both molecular terminals (terminals ofchain molecule or molecular chain) thereof, for example, a curableorganopolysiloxane having both molecular chain terminals thereof blockedwith silanol groups (≡Si—OH) is used as the component (A), it isespecially preferred that the component (A) be used in combination withthe component (C) as a crosslinking agent/curable agent. Further, when,for example, a curable organopolysiloxane having both molecularterminals thereof blocked with hydrolyzable groups is used as thecomponent (A), it is also preferred that the composition, althoughsatisfactorily curable in the absence of the component (C) as a curableagent, contain the component (C).

The above X represents the same hydrolyzable group as represented by Wof the formula [α].

The organosilane represented by the formula [I] or (partial) hydrolyzatethereof can be, for example, any of methyltrimethoxysilane,methyltri(methylethylketoxime)silane, methyltripropenyloxysilane andmethyltriacetoxysilane, any of silane compounds obtained bysubstituting, for example, vinyl, phenyl or trifluoropropyl for methylof the above silane compounds, and partial hydrolyzates thereof. Withrespect to these compounds, the hydrolyzable group is preferably aketoxime group.

Each of these organosilanes or hydrolyzates thereof (C), although can becontained in an amount of 1 to 60 parts by weight, are generallypreferably contained in the curable composition of the present inventionin an amount of 1 to 20 parts by weight, still preferably 2 to 10 partsby weight per 100 parts by weight of the organopolysiloxane (A).

When these organosilanes or hydrolyzates thereof (C) are contained inthe curable composition in the above amount, crosslinking reaction ofthe component (A) is appropriately advanced, and the obtained coatingfilm tends to have appropriate hardness, ensuring economic advantages.

Silicone Oil (D)

The curable composition of the present invention may contain siliconeoil (D). Although the silicone oil (D) is not particularly limited aslong as it is a nonreactive (noncondensable) silicone oil or a siliconeoil which bleeds out from a cured product of the curable composition, itis preferred that use be made of silicone oil (D) different from thecomponent (A), silicone oils represented by the following formulae [II]and [IV] and silicone oils having groups represented by the followingformula [III].

Among these silicone oils (D), the silicone oils of the formulae [II]and [IV] would not be reactive with, for example, the component (A),would not be self-condensable and would have the function of forming anantifouling layer (film) at the surface (surface layer) of the coatingfilm. On the other hand, the silicone oils with groups [III] would reactwith, for example, the component (A) constituting a coating film formingcomponent to thereby form a cured coating film, would be hydrolyzed withthe passage of time while being immersed in sea water for a prolongedperiod of time so that the terminal groups are converted into groupshaving an alcoholic hydroxyl group such as [≡SiR⁴OH], and thus wouldbleed out from the surface of the coating film to thereby exert aneffect of preventing the sticking of sea lives.

(R²)₃SiO(SiR³ ₂O)_(n)Si(R²)₃  Formula [II]

wherein the groups R² may be identical with or different from eachother, and each thereof represents a 1 to 10 carbon atoms having alkyl,aryl, aralkyl or fluoroalkyl; the groups R³ may be identical with ordifferent from each other, and each thereof represents a 1 to 10 carbonatoms having alkyl, aryl, aralkyl or fluoroalkyl; and n is a number of 0to 150.

≡SiR⁴OSiR⁵ _(b)Y_(3−b)  Formula [III]

wherein R⁴ represents an unsubstituted or substituted divalenthydrocarbon group or a divalent hydrocarbon group containing an etherbond; R⁵ represents an unsubstituted or substituted monovalenthydrocarbon group; Y represents a hydrolyzable group; and b is 0, 1 or2.

R⁶ _(x)Si(R⁷—Z)_(y)O_((4−x−y)/2)  Formula [IV]

wherein R⁶ represents a hydrogen atom or any of an alkyl group, an arylgroup and an aralkyl group, these groups each having 1 to 10 carbonatoms; R⁷ represents an ether group, an ester group or a divalentaliphatic hydrocarbon group having 1 to 10 carbon atoms between which—NH— may be present; Z represents a monovalent polar group selected fromamong an amino group, a carboxyl group, an epoxy group and apolyethylene glycol or polypropylene glycol group whose terminal may beblocked with a 1 to 6 carbon atoms having alkyl or acyl; and x and ysatisfy the relationships: 0.01≦x<3.99, 0.02≦y<4 and 0.02≦x+y<4.

Among the silicone oils (D), the silicone oils of the formula [II] maybe those described in Japanese Patent Laid-open Publication No.10(1998)-316933. It is preferred that the number average molecularweight thereof range from 180 to 20,000, especially from 1000 to 10,000,and that the viscosity thereof range from 20 to 30,000 centistokes,especially from 50 to 3,000 centistokes.

Examples of the silicone oils of the formula [II] includedimethylsilicone oils as represented by the formula [II] wherein all thegroups R² and R³ are methyl, and methylphenylsilicone oils correspondingto the dimethylsilicone oil whose methyl groups are partially replacedby phenyl. Methylphenylsilicone oils are preferred.

The above methylphenylsilicone oils are commercially available by thetradename of, for example, “KF-54”, “KF-56” and “KF-50” (products ofShin-Etsu chemical Co., Ltd.), “SH510” and “SH550” (products of DowCorning Toray Silicone Co., Ltd.) or “TSF431” and “TSF433” (products ofToshiba Silicone Co., Ltd.).

Those described in Japanese Patent No. 2,522,854 granted on theinvention formerly proposed by the same applicants can be used as thesilicone oils having groups represented by the above formula [III](simply referred to as “silicone oils [III]”). It is preferred that thenumber average molecular weight thereof range from 250 to 20,000,especially from 1000 to 10,000, and that the viscosity thereof rangefrom 20 to 30,000 centistokes, especially from 50 to 3000 centistokes.

≡SiR⁴OSiR⁵ _(b)Y_(3−b)  Formula [III]

wherein R⁴ represents an unsubstituted or substituted divalenthydrocarbon group or a divalent hydrocarbon group containing an etherbond; R⁵ represents an unsubstituted or substituted monovalenthydrocarbon group; Y represents a hydrolyzable group; and b is 0, 1 or2.

The group R⁴ is, for example, an unsubstituted or substituted divalenthydrocarbon group such as methylene, ethylene, propylene, butylene orhexamethylene, or a divalent hydrocarbon group containing an ether bondas represented by the formula —(CH₂)_(p)—O—(CH₂)_(q)— (wherein each of pand q independently is an integer of 1 to 6).

The group R⁵ is, for example, the same unsubstituted or substitutedmonovalent hydrocarbon group having 1 to 8 carbon atoms as representedby R¹ of the formula [I] for the above component (C). The group Y is,for example, the same hydrolyzable group as represented by X of theformula [I] for the above component (C).

The silicone oils [III], i.e., silicone oils having at least one grouprepresented by the formula [III] can be, for example, silicone oilshaving hydroxyls thereof blocked with hydrolyzable groups, representedby the formulae:

(CH₃)₃SiO[(CH₃)₂SiO]_(m)[R⁷R⁸SiO]_(n)(CH₃)₂SiC₃H₆—OH,

HO—C₃H₆—[(CH₃)₂SiO][(CH₃)₂SiO]_(m)[R⁷R⁸SiO]_(n)—(CH₃)₂Si—C₃H₆—OH, and

(CH₃)₃SiO[(CH₃)₂SiO]_(m)[R⁷R⁸SiO]_(n)[(CH₃)(C₃H₆—OH)SiO]_(l)[(CH₃)₂SiCH₃],

as described in the above Japanese Patent No. 2,522,854. In the aboveformulae, R⁷ and R⁸ represent unsubstituted or substituted monovalenthydrocarbon groups selected from among aryl groups such as phenyl andtolyl, aralkyl groups such as benzyl and β-phenylethyl, and halogenatedalkyl groups such as trifluoropropyl, provided that at least one of R⁷and R⁸ is not methyl; and m, n and l are all integers.

Further, from the viewpoint of the storage stability of the finalcomposition, the silicone oils [III] can be those obtained by reactingthe above silicone oils with organosilanes represented by the formula:R⁵ _(b)SiY_(3−b) (wherein R⁵, Y and b are as defined in the formula[III]), for example, as follows:

(CH₃)₃SiO[(CH₃)₂SiO]_(m)[R⁷R⁸SiO]_(n)(CH₃)₂SiC₃H₆—O—R⁵ _(b)SiY_(3−b),

HO—C₃H₆—[(CH₃)₂SiO][(CH₃)₂SiO]_(m)[R⁷R⁸SiO]_(n)—(CH₃)₂Si—C₃H_(6—O—R) ⁵_(b)SiY_(3−b), and

(CH₃)₃SiO[(CH₃)₂SiO]_(m)[R⁷R⁸SiO]_(n)[(CH₃)(C₃H₆—O—R⁵_(b)—SiY_(3−b))SiO]_(l)[(CH₃)₂SiCH₃].

The silicone oils of the formula [IV] can be, for example, thosedescribed in Japanese Patent Laid-open Publication No. 10(1998)-316933.It is preferred that the number average molecular weight thereof rangefrom 250 to 30,000, especially from 1000 to 20,000, and that theviscosity thereof range from 20 to 30,000 centistokes, especially from50 to 3,000 centistokes.

R⁶ _(x)Si(R⁷—Z)_(y)O_((4−x−y)/2)  Formula [IV]

wherein R⁶ represents a hydrogen atom or any of an alkyl group, an arylgroup and an aralkyl group, these groups each having 1 to 10 carbonatoms; R⁷ represents an ether group, an ester group or a divalentaliphatic hydrocarbon group having 1 to 10 carbon atoms between which—NH— may be present; Z represents a monovalent polar group selected fromamong an amino group, a carboxyl group, an epoxy group and apolyethylene glycol or polypropylene glycol group whose terminal may beblocked with a 1 to 6 carbon atoms having alkyl or acyl; and x and ysatisfy the relationships: 0.01≦x<3.99, 0.02 ≦y<4 and 0.02≦x+y<4.

The silicone oils of the formula [IV] are preferably those representedby the formula [IV] wherein R⁶ represents methyl or phenyl and R⁷represents methylene, ethylene or propylene. When Z represents apolyethylene glycol or polypropylene glycol group whose terminal may beblocked with an up to 6 carbon atoms having alkyl or acyl, the number ofoxyethylene units or oxypropylene units as repeating units in the grouppreferably ranges from 10 to 60. The above alkyl for terminal blockingcan be, for example, any of methyl, ethyl, propyl and butyl, and theabove acyl for terminal blocking can be, for example, any of ketoxime,acetyl and propionyl.

Examples of the silicone oils of the formula [IV] wherein the polargroup Z is an amino group include “SF8417” (produced by Dow CorningToray Silicone Co., Ltd.), “ISI4700” and “ISI4701” (produced by ToshibaSilicone Co., Ltd.) and “FZ3712” and “AFL-40” (produced by Nippon UnicarCompany, Limited). Examples of the silicone oils of the formula [IV]wherein the polar group Z is a carboxyl group include “XI42-411”(produced by Toshiba Silicone Co., Ltd.), “SF8418” (produced by DowCorning Toray Silicone Co., Ltd.), and “FXZ4707” (produced by NipponUnicar Company, Limited). Examples of the silicone oils of the formula[IV] wherein the polar group Z is an epoxy group include “SF8411”(produced by Dow Corning Toray Silicone Co., Ltd.), “XI42-301” (producedby Toshiba Silicone Co., Ltd.) and “L-93” and “T-29” (produced by NipponUnicar Company, Limited). Examples of the silicone oils of the formula[IV] wherein the polar group Z is an alkyl or acyl include “ISI4460”,“ISI4445” and “ISI4446” (produced by Toshiba Silicone Co., Ltd.),“SH3746”, “SH8400”, “SH3749” and “SH3700” (produced by Dow Corning ToraySilicone Co., Ltd.), and “KF6009” (produced by Shin-Etsu Silicone Co.,Ltd.).

In the present invention, the silicone oil (D), preferably at least oneof the silicone oil [II], silicone oil [III] and silicone oil [IV], ispreferably contained in the composition in a total amount of 0.1 to 200parts by weight, still preferably 20 to 100 parts by weight, per 100parts by weight of the component (A).

When the amount of the silicone oil (D) falls within the above range,there is a tendency to form, for example, in the use as an antifoulingpaint, an (antifouling) coating film being excellent in both ofantifouling properties and coating film strength. When the amount of thesilicone oil (D) is less than the above range, the antifoulingproperties may be deteriorated. On the other hand, when the amount ofthe silicone oil (D) exceeds the above range, the strength of thecoating film may be reduced.

Production of Curable Composition

The first curable composition of the present invention, especially thecoating composition, curable paint composition or antifouling paintcomposition, can be produced by first heating part or all of thecomponent (A) together with at least the hydrophilic silica, preferablyboth of the hydrophilic silica and the hydrophobic silica, among thecomponents (B-1) under the atmospheric pressure or a reduced pressure ata temperature which is 100° C. or over but below the decompositiontemperatures of the components, preferably from 100 to 300° C., andstill preferably about 140 to 200° C., for a period generally from 30min to 3 hr, and thereafter adding thereto any remainder of thecomponent (A) and any remainder of the component (B-1) optionallytogether with the component (C) and the component (D). The secondcurable composition of the present invention can be produced by firstheating part or all of the component (A) together with the hydrophobicsilica as the silica component (B-2) under the same pressure at the sametemperature for the same period as effected in the production of thefirst curable composition, and thereafter adding thereto any remainderof the component (A) optionally together with the component (C) and thecomponent (D).

The heating of at least the hydrophilic silica, preferably both of thehydrophilic silica and the hydrophobic silica, among the components(B-1) together with the component (A) in the first invention and theheating of the hydrophobic silica as the component (B-2) together withthe component (A) in the second invention enable avoiding aggregation ofthe component (B-1) or (B-2) as a filler component because of the highaffinity between the component (A) and the filler component in theobtained composition. Therefore, the final coating composition, forexample, the antifouling paint composition has appropriate fluidity andthixotropy to thereby enable forming a coating film of desirably largethickness even on a vertical surface by one-time or a few applicationsthereof.

In the agitation and mixing of the above added components, appropriateuse is made of common mixers and agitators such as Ross mixer, planetarymixer and universal Shinagawa agitator.

For example, catalysts described in Japanese Patent No. 2,522,854 canappropriately be used as the above catalyst of the present invention,examples of which include:

tin carboxylates such as tin naphthenate and tin oleate;

tin compounds such as dibutyltin diacetate, dibutyltin dioctoate,dibutyltin dilaurate, dibutyltin dioleate, dibutyltin oxide, dibutyltindimethoxide and dibutylbis(triethoxysiloxy)tin;

titanates and titanium chelate compounds such astetraisopropoxytitanium, tetra-n-butoxytitanium,tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titaniumand titanium isopropoxyoctyl glycol;

organometallic compounds such as zinc naphthenate, zinc stearate, zinc2-ethyloctoate, iron 2-ethylhexoate, cobalt 2-ethylhexoate, manganese2-ethylhexoate, cobalt naphthenate and alkoxyaluminum compounds;

alkoxysilanes substituted with aminoalkyl groups such as3-aminopropyltrimethoxysilane,N-β-aminoethyl-γ-aminopropyltrimethoxysilane;

amine compounds and salts thereof such as hexylamine,dodecyldodecylamine phosphate, dimethylhydroxylamine anddiethylhydroxylamine;

quaternary ammonium salts such as benzyltriethylammonium acetate;

lower fatty acid salts of alkali metals such as potassium acetate,sodium acetate and lithium oxalate; and

guanidino containing silanes and siloxanes such astetramethylguanidinopropyltrimethoxysilane,tetramethylguanidinopropylmethyldimethoxysilane andtetramethylguanidinopropyltris(trimethylsiloxy)silane.

These catalysts are used in an amount of not greater than 10 parts byweight, preferably not greater than 5 parts by weight, and stillpreferably not greater than 1 parts by weight, per 100 parts by weightof the component (A). The preferred lower limit of these catalysts is0.001 part by weight, especially 0.01 part by weight.

<Optional Component>

The curable composition of the present invention, when used as, forexample, a coating composition, especially a paint composition or anantifouling paint composition, still especially a curable antifoulingpaint composition (antifouling paint), may be optionally loaded with thebelow described antifouling agents, plasticizers, inorganic dehydratingagents (stabilizers), metal salts of carboxylic acids,antisagging/antisetting agents (thixotropic agents), pigments, othercoating film forming components, other fillers, fire retardants,thixotropic agents, heat conduction improvers, solvents, mildewproofingagents, germicides, flatting agents, perfumes and the like, in additionto the above essential components (A) and (B-1) or (B-2) and optionalcomponents (C) and (D).

<Antifouling Agents>

Both inorganic and organic antifouling agents can be used. Althoughcommon inorganic antifouling agents can be used, copper and inorganiccopper compounds are especially preferred.

Organic Antifouling Agents

Examples of the organic antifouling agents include metal-pyrithionecompounds of the formula:

wherein each of R¹ to R⁴ independently represents a hydrogen atom, analkyl group, an alkoxy group or a halogenated alkyl group; M representsa metal such as Cu, Zn, Na, Mg, Ca, Ba, Pb, Fe or Al; and n is avalence,

and further include tetramethylthiuram disulfide, carbamate compounds(e.g., zinc dimethyldithiocarbamate and manganese2-ethylenebisdithiocarbamate), 2,4,5,6-tetrachloroisophthalonitrile,N,N-dimethyldichlorophenylurea,4,5-dichloro-2-n-octyl-3(2H)isothiazoline,2,4,6-trichlorophenylmaleimide and2-methylthio-4-t-butylamino-6-cyclopropyl-s-triazine.

Of the above organic antifouling agents, copper pyrithione (in theformula (vi), M=Cu), zinc pyrithione (in the formula (vi), M=Zn),N,N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide,2-methylthio-4-t-butylamino-6-cyclopropyl-s-triazine,4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and2,4,5,6-tetrachloroisophthalonitrile are preferred.

Of these organic antifouling agents, metal pyrithiones and/or4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is still preferred, thejoint use thereof yet still preferred because excellent antifoulingcapability can be exhibited. In particular, the use of copper pyrithioneand/or 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is especiallypreferred, the joint use thereof yet especially preferred.

In the antifouling paint compositions containing these organicantifouling agents, for example, it is generally preferred that, besidesthe copper and/or inorganic copper compounds, the organic antifoulingagent be contained in an amount of 0.1 to 20% by weight, especially 0.5to 10% by weight. Per 100 parts by weight of solid contents of the paintcomposition, it is generally preferred that the organic antifoulingagent in terms of solid be contained in an amount of 0.1 to 150 parts byweight, especially 0.1 to 100 parts by weight.

<Plasticizer (Chlorinated Paraffin)>

Examples of the plasticizers include TCP (tricresyl phosphate),chlorinated paraffin and polyvinyl ethyl ether. These plasticizers canbe used either individually or in combination.

These plasticizers contribute to enhancement of the crack resistance ofthe coating film composed of obtained antifouling paint composition(also referred to as “antifouling coating film”).

<Inorganic Dehydrating Agent>

The inorganic dehydrating agents also function as a stabilizer tothereby enable enhancing the storage stability of the final antifoulingpaint composition. Examples of the inorganic dehydrating agents includeanhydrous gypsum (CaSO₄), synthetic zeolite adsorbents (trade name:Molecular Sieve, etc.) and silicates, of which anhydrous gypsum andMolecular Sieve are preferably employed. These inorganic dehydratingagents can be used either individually or in combination.

With respect to the curable paint compositions containing theseinorganic dehydrating agents, the inorganic dehydrating agent maygenerally be contained in the nonstannous paint composition of thepresent invention in an amount of 0.1 to 10% by weight, preferably about0.1 to 5% by weight.

<Metal Salt of Carboxylic Acid>

The curable paint composition of the present invention may furthercontain metal salts of carboxylic acids.

Use is made of carboxylic acid metal salts whose molecular weight isgenerally in the range of 50 to 1000, preferably 100 to 600.

Carboxylic acids constituting these carboxylic acid metal salts can be,for example, carboxylic acids with an alicyclic structure (e.g.,naphthenic acid), carboxylic acids with an aromatic ring structure(e.g., α-(2-carboxyphenoxy)stearic acid), rosin resin acids and fattyacids. Of these, naphthenic acid, rosin resin acids and fatty acids arepreferred.

<Antisagging/antisetting Agent (Thixotropic Agent)>

Examples of the antisagging/antisetting agents (thixotropic agents)include organic clay salts such as stearate, lecithinate, alkylsulfonatesalts of Al, Ca and Zn, and further include polyethylene wax, amide wax,hydrogenated castor oil wax, polyamide wax, a mixture of hydrogenatedcastor oil wax and polyamide wax, synthetic particulate silica andpolyethylene oxide wax. Of these, polyamide wax, synthetic particulatesilica, polyethylene oxide wax and organic clay salts are preferablyemployed. As the antisagging/antisetting agents, use can also be made ofthose commercially available, for example, by the trade names “Disparlon305”, “Disparlon 4200-20” and “Disparlon A632-20X”, all products ofKusumoto Chemicals, Ltd.

These antisagging/antisetting agents are added to the curable paintcomposition in an amount of, for example, 0.1 to 10% by weight.

<Pigment>

Use can be made of various common organic and inorganic pigments.

Examples of the organic pigments include carbon black, PhthalocyanineBlue and Prussian Blue. Examples of the inorganic pigments include thosewhich are neutral and nonreactive, such as titanium white, red ironoxide, baryta powder, silica, calcium carbonate, talc, whiting (chalk)and iron oxide powder; and those (active pigments) which are basic andreact with acidic substances in the paint, such as zinc oxide (ZnO),white lead, red lead, zinc powder and lead suboxide powder. Dyes andother various colorants may be contained in the pigments. These variouspigments are added to the curable composition, especially the curablepaint composition, in a total amount of, for example, about 0.5 to 45%by weight.

<Other Coating Film Forming Component>

Coating film forming components other than the above organopolysiloxane(A), etc. may be contained in the curable composition as long as it isnot detrimental to the object of the present invention. Examples of theother coating film forming components include slightly water-soluble ornon-water-soluble resins (hereinafter also referred to as“slightly/non-water-soluble resins”) such as acrylic resin, acrylicsilicone resin, unsaturated polyester resins, fluororesins, polybuteneresin, silicone rubber, urethane resin (rubber), polyamide resins, vinylchloride copolymer resins, chlorinated rubber (resin), chlorinatedolefin resins, styrene/butadiene copolymer resin, ethylene/vinyl acetatecopolymer resin, vinyl chloride resin, alkyd resin, cumarone resin,trialkylsilyl acrylate (co)polymers (silyl resins) and petroleum resin.

<Other Filler, Fire Retardant, Thixotropic Agent, Heat ConductionImprover and Adhesive Component>

Examples of the other fillers than mentioned above include:

metal oxides such as diatom earth, iron oxide, zinc oxide, titaniumoxide and alumina, and substances obtained by treating the surface ofthese with silane compounds;

metal carbonates such as calcium carbonate, magnesium carbonate and zinccarbonate; and

other materials such as asbestos, glass fiber, carbon black, quartzpowder, aluminum hydroxide, gold powder, silver powder, calciumcarbonate with its surface treated and glass balloon. These fillers maybe used either individually or in combination.

Examples of the thixotropic agents include polyethylene glycol,polypropylene glycol and derivatives thereof.

Examples of the fire retardants include antimony oxide and paraffinoxide.

Examples of the heat conduction improvers include boron nitride andaluminum oxide.

Examples of the adhesive components include silane coupling agentshaving at least one alkoxysilyl group, epoxy group, hydrosilyl group,(meth)acrylic group, hydroxysilyl group or like group, like substancesand mixtures thereof.

<Solvent>

Although solvents may be contained or absent in the curable compositionsuch as the curable paint composition according to the presentinvention, the above various components can be dissolved or dispersed insolvents before use according to necessity. Use can be made of varioussolvents commonly added to antifouling paints, such as aliphatic,aromatic, ketonic, ester, ether and alcoholic solvents. Examples of thearomatic solvents include xylene and toluene. Examples of the ketonicsolvents include MIBK and cyclohexanone. Examples of the ether solventsinclude propylene glycol monomethyl ether and propylene glycolmonomethyl ether acetate (PMAC). Examples of the alcoholic solventsinclude isopropyl alcohol.

These solvents, although can be used in an arbitrary amount, are, forexample, added to the curable composition in an amount of 0.1 to 9999parts by weight, preferably 1 to 50 parts by weight, per 100 parts byweight of the component (A). The solvents are used in such an amountthat the proportion thereof to the curable composition of the presentinvention is in the range of 1 to 99% by weight, preferably 5 to 50% byweight.

The viscosity (25° C., Brookfield viscometer, rotor No. 3) of thecurable composition such as the curable paint composition optionallydiluted with the above solvents, taking into account the applicability(sagging properties) and the thickness of coating film obtained byone-time application, is, for example, in the range of about 0.01 to 500P(poise)/25° C., preferably 0.1 to 200 P/25° C., that is, in the rangeof about 0.001 to 50 Pa·s, preferably 0.01 to 20 Pa·s.

The curable composition of the present invention is suitable for use asa coating material (coating composition) applied to various basematerials such as an electrical part, an electronic part, a buildingmaterial, a craftwork object, a fashion industry supply and a medicalsupply in order to cover the surface thereof. Further, the curablecomposition is suitable for use as an antifouling paint applied to basematerials brought into contact with sea water or fresh water, such as anunderwater structure, a ship shell plate, a fishing net and a fishinggear, in order to render the surface thereof antifouling. Still further,the curable composition is used as a de-icing paint, a water repellentor the like. Thus, the curable composition of the present inventionfinds applicability in a wide range of industrial fields such aselectricity/electronics, building material/craftwork, apparel industry,medical treatment, agriculture/forestry/fishery, electric powerproduction, harbor/civil engineering construction, shipbuilding, shiprepair (especially ship painting), etc.

In particular, in the application and curing the above curablecomposition as a coating composition to the surface of base materialssuch as an electrical part, an electronic part, a building material, acraftwork object, an apparel industry supply and a medical supply, thecurable composition exhibits an excellent balance of low viscosity andhigh thixotropy to thereby enable forming a thick coating film byone-time application. Thus, the curable composition ensures high coatingoperation efficiency. The application and curing the curable compositionprovides base materials covered with coating films which are excellentin, for example, fire retardation, rubber strength and surfacesmoothness.

Also, in particular, the above curable composition can be applied as apaint, especially an antifouling paint (antifouling paint composition),to the surface of various shaped items such as underwater structures,for example, supply water inlets and waste water outlets for thermalpower plants and nuclear power plants, sea water utilizing apparatus(e.g., sea water pump), megafloats, coastal roads, undersea tunnels,harbor facilities, sludge diffusion preventive membranes for use invarious marine civil engineering works such as canals and waterways,ships (especially ship shell plates) and fishing materials (e.g., rope,fishing net, float and buoy) once or a plurality of times according tothe customary technique and cured. As a result, there can be obtainedantifouling base materials, such as ships and underwater structures,covered with the antifouling coating film which is excellent inantifouling properties and can slowly release the antifouling agentcomponent for a prolonged period of time and which, despite the thickcoating, has appropriate flexibility with excellent crack resistance. Inthe application of the curable composition, use is made of a widevariety of common coating techniques such as brush, roll, spray and dipcoater.

The antifouling coating film obtained by applying the above curableantifouling paint composition of the present invention to the surface ofvarious shaped items (base materials) and curing the same is excellentin antifouling properties and, for example, can continuously inhibitsticking of aquatic organisms such as sea lettuces, barnacles, greenlavers, serpulas, oysters and Bugula for a prolonged period of time.

When, for example, the supply water inlets and waste water outlets fornuclear power plants, megafloats and ships are made of FRP, steel, wood,aluminum alloy and the like, the curable antifouling paint compositionparticularly effectively adheres to the surface of these base materials.This curable antifouling paint composition may be applied as an overcoatto the surface of any existing antifouling coating films.

Moreover, for example, the application and curing the curableantifouling paint composition to the surface of undersea structuresenables inhibiting the sticking of sea lives so that the capability ofthe undersea structures can be maintained for a prolonged period oftime. The application and curing the curable antifouling paintcomposition to the surface of fishing nets enables avoiding the cloggingof the meshes of the fishing nets while ensuring a reduced danger ofenvironmental pollution.

The curable antifouling paint composition of the present invention maybe directly applied to fishing nets, or may be applied to the surface ofships, underwater structures and the like which has been furnished withan undercoat such as a rust preventive agent or a primer. Furthermore,the curable antifouling paint composition of the present invention maybe applied as an overcoat for repair to the surface of ships, especiallyFRP ships, underwater structures and the like which has already beencoated with conventional antifouling paints or the curable antifoulingpaint composition of the present invention. The thickness of theantifouling coating film thus formed on the surface of the ships,underwater structures and the like, although not particularly limited,is, for example, in the range of about 30 to 150 μm per application.

The thus obtained antifouling coating film, or coating film on thesurface of parts of ships and underwater structures brought into contactwith water, according to the present invention is formed from the abovecurable antifouling paint composition, ensures a reduced danger ofenvironmental pollution and is excellent in the long-term antifoulingcapability against a wide variety of organisms which adhere to ships andunderwater structures.

EFFECT OF THE INVENTION

The curable composition of the present invention, when used as a coatingcomposition, especially a paint, an antifouling paint composition or thelike, realizes an excellent balance of low viscosity and high thixotropyand exhibits excellent sprayability, for example, free from nozzleclogging and turbulence. The curable composition enables forming a thickcoating film by one-time application to thereby enable shortening theoperating period for coating. A coating film or other cured product,which is excellent in the uniformity of coating film surface (uniformityof coating film thickness and surface smoothness), can be obtained bythe application thereof. Moreover, the obtained coating film is alsoexcellent in film strength (rubber strength) and film hardness. In theuse as an antifouling paint, the obtained coating film can exertexcellent antifouling capability for a prolonged period of time.Furthermore, the curable composition ensures excellent storage stabilitybefore application thereof. Thus, there is provided the coatingcomposition, especially curable composition which is suitable for use asa curable paint composition, an antifouling paint composition or thelike.

Further, according to the present invention, there are provided not onlythe coating film, coating composition cured product and other variouscured products (especially antifouling coating film), which, asmentioned above, are excellent in film strength and film hardness andwhich exert excellent antifouling capability for a prolonged period oftime but also, for example, the underwater structure and ship shellplate covered with the coating film to thereby possess thesecharacteristics.

Still further, according to the present invention, there are providedthe method of forming a coating film on the surface of a base materialsuch as an electronic part and the method of rendering antifouling thesurface of a base material such as an underwater structure, wherein, forexample, the above coating film with excellent properties canefficiently formed on the surface of various base materials such as anunderwater structure in a manner ensuring worker's safety and free fromthe danger of environmental pollution.

EXAMPLE

The present invention will further be illustrated below with referenceto the following Examples and Comparative Examples, which in no waylimit the scope of the invention.

In the following Synthetic Examples, Working Examples and ComparativeExamples, compositions are described in terms of parts by weight unlessotherwise specified.

Synthesis of Silicone Oil (D) Synthetic Example 1

193 g of organopolysiloxane having an alcoholic hydroxyl group,represented by the formula:

was mixed with 60 g of methyltri(methylethylketoxime)silane at roomtemperature and reacted, thereby obtaining silicone oil (D) of theformula:

This silicone oil contained unreacted starting compoundmethyltri(methylethylketoxime)silane.

[Preparation of Organopolysiloxane Paint Compositions (1A) to (1F)Specified in Table 1]

Component (refer to *2) obtained by subjecting dimethylpolysiloxanehaving both molecular terminals thereof blocked with silanol groupswhose viscosity was 20,000 cSt, as organopolysiloxane, and hydrophobicfumed silica having its surface treated with hexamethyldisilazane tomixing and agitation at 150° C. for 2 hr to thereby effect thermaltreatment, component (refer to *3) obtained by subjecting thehydrophobic silica indicated in Table 1 and the organopolysiloxane tomixing and agitation at room temperature and component (refer to *4)obtained by subjecting the hydrophilic silica indicated in Table 1 andthe organopolysiloxane to mixing and agitation 150° C. for 2 hr tothereby effect thermal treatment were blended together in proportionsindicated in Table 1, and satisfactorily mixed by means of an agitatorso that homogeneous dispersions were obtained. Further, the crosslinkingagent and catalyst were added in proportions indicated in Table 1 andhomogeneously mixed. Thus, room-temperature-curable organopolysiloxanepaint compositions of formulations (1A) to (1F) were obtained.

The property values of these compositions are listed in Table 1. InTable 1, *1, *2, *3 and *4 have the following meanings, and the testingmethods are as described below.

Further, in the table, the amount of various silicas is expressed byparts by weight per 100 parts by weight of organopolysiloxane (A).

*1: Organopolysiloxane: produced by Shin-Etsu Chemical Co., Ltd.

represented by the formula: HO(CH₃)₂SiO)_(m)H (viscosity at 25° C.:20,000 cSt).

*2: Thermally treated hydrophobic fumed silica:

silica obtained by subjecting the hydrophobic fumed silica indicated inTable 1 and the above organopolysiloxane to mixing and agitation 150° C.for 2 hr to thereby effect thermal treatment (produced by Shin-EtsuChemical Co., Ltd., water content of silica: 0.05%, bulk density: 50g/lit., primary particle diameter: 10 mμ, and specific surface area (interms of BET): 180 m²/g).

*3: Room-temperature-treated hydrophobic fumed silica:

silica obtained by subjecting the hydrophobic fumed silica indicated inTable 1 and the above organopolysiloxane to mixing and agitation at roomtemperature (produced by Shin-Etsu Chemical Co., Ltd., water content:0.2%, bulk density: 50 g/lit., primary particle diameter: 10 mμ, andspecific surface area (in terms of BET): 180 m²/g).

*4: Thermally treated hydrophilic silica:

silica obtained by subjecting the hydrophilic silica indicated in Table1 and the above organopolysiloxane to mixing and agitation 150° C. for 2hr to thereby effect thermal treatment (produced by Shin-Etsu ChemicalCo., Ltd., water content: 1.0%, bulk density: 60 g/lit., primaryparticle diameter: 12 mμ, and specific surface area (in terms of BET):190 m²/g).

[Testing Method]

(a) Viscosity:

The viscosity (Pa·s/25° C.) of the obtained organopolysiloxane paintcompositions as specified in Table 1 was measured by the use ofBrookfield viscometer (rotor No. 3).

(b) Physical Characteristics of Coating Film:

The physical characteristics of coating film were determined withrespect to the coating films of 2 mm thickness prepared by applying eachof the organopolysiloxane paint compositions (1A) to (1F) onto astainless steel plate and allowing it to stand still at 25° C. in 55% RHfor 7 days to thereby effect curing thereof.

Results are given in Table 1.

TABLE 1 Organopolysiloxane paint composition Example Comp. Ex. 1A 1B 1C1D 1E 1F organopolysiloxane *1 0 0 0 0 50 50 thermally treatedhydrophobic fumed silica mixture *2 60 90 60 30 (hydrophobic fumedsilica *5) (10) (15) (10)  (5) (organopolysiloxane *6) (50) (75) (50)(25) room temp. treated hydrophobic fumed silica mixture *3 70(hydrophobic fumed silica *5) (20) (organopolysiloxane *6) (50)thermally treated hydrophilic silica mixture *4) 60 30 60 90 70(hydrophilic silica *5) (10)  (5) (10) (15) (20) (organopolysiloxane *6)(50) (25) (50) (75) (50) (total organopolysiloxane (A) component incompsn.) (100)  (100)  (100)  (100)  (100)  (100) methyltri(methylethylketoxime) silane 10 10 10 10 methyltriacetoxysilane7 7 dibutyltin dilaurate 0.1 0.1 0.1 0.1 0.1 0.1 xylene 20 20 20 20 2020 properties viscosity (Pa · s/25° C.) 0.7 0.8 0.7 0.6 0.8 0.5 specificgravity (20° C.) 0.99 0.99 0.99 0.99 0.99 0.98 physical characteristicof film hardness (JIS-K) 45 47 46 42 39 24 tensile strength (MPa) 3.53.6 3.5 3.3 2.9 2.0 elongation (%) 230 210 230 250 170 190 *1, 2, 3, 4,5: produced by Shin-Etsu Chemical Co., Ltd. *1: organopolysiloxane(weight) added at the time of composition preparation. *2, 3, 4: numericvalue indicates the addition amount (weight) ofsilica/organopolysiloxane treatment product. *5: silica (weight)contained in silica/organopolysiloxane treatment product. *6:organopolysiloxane (weight) contained in silica/organopolysiloxanetreatment product.

Examples 1 to 4 and Comparative Examples 1 and 2

Silicone oil and xylene were added in amounts indicated in Table 2 to100 parts by weight of each of the obtained organopolysiloxane paintcompositions (1A) to (1F) as specified in Table 1, and mixed andagitated until becoming homogeneous. Thus, antifouling paintcompositions were obtained.

With respect to each of the antifouling paint compositions, theproperties and applicability were determined.

Results are given in Table 2.

Further, an antifouling test was performed with respect to each of theantifouling paint compositions immediately after the preparationthereof.

Results are given in Table 3.

In Table 2, *7, *8, *9 and *10 have the following meanings, and thetesting methods are as described below. The parenthesized amount ofvarious silicone oils is parts by weight added per 100 parts by weightof organopolysiloxane (A).

*7 SH550: dimethylphenylsilicone oil, viscosity: 130 centistokes,produced by Dow Corning Toray Silicone Co., Ltd.

*8 TSF431: dimethylphenylsilicone oil, viscosity: 100 centistokes,produced by Toshiba Silicone Co., Ltd.

*9 KF50: dimethylphenylsilicone oil, viscosity: 100 centistokes,produced by Shin-Etsu Chemical Co., Ltd.

*10 KF6016: polyether modified silicone oil, viscosity: 150 centistokes,produced by Shin-Etsu Chemical Co., Ltd.

TABLE 2 Example 1 Example 2 Example 3 Example 4 Comp. Ex. 1 Comp. Ex. 2organopolysiloxane (paint) cmpsn. type 1A 1B 1C 1D 1E 1F amt. 100 100100 100 100 100 silicone oil SH550 *7 TSF431 *8 60 (64) 70 (75) 40 (43)KF50 *9 80 (85) 60 (64) 30 (32) 30 (32) silicone oil of Synthetic Ex. 130 (32) 40 (43) KF-6016 *10 10 (11) xylene 10 10 10 10 10 10 propertiesof paint viscosity (Pa · s/25° C.) 0.4 0.5 0.3 0.3 0.5 0.2 specificgravity (20° C.) 0.99 0.99 0.99 0.99 0.99 0.99 applicabilitysprayability good good good good good good sagging (limit film thicknessμm) 180 170 180 160 160 130 after 3 months at 50° C. condition of paint(stability) normal normal normal normal gelatinized gelatinizedsprayability good good good good clogged clogged sagging (limit filmthickness μm) 180 170 180 160 140 110 *7: produced by Dow Corning ToraySilicone Co., Ltd. *8: produced by Toshiba Silicone Co., Ltd. *9:produced by Shin-Etsu Chemical Co., Ltd. *10: produced by Shin-EtsuChemical Co., Ltd. Note: parenthesized amount of silicone oils indicatesthe addition amount (pts. wt.) per 100 parts by weight oforganopolysiloxane (A).

TABLE 3 Example 1 Example 2 Example 3 Example 4 Comp. Ex. 1 Comp. Ex. 2antifouling property  6 months normal normal normal normal normal normal12 months normal normal normal normal normal normal 18 months normalnormal normal normal normal slime slightly adhered 24 months normalnormal normal normal slime/ slime/ shellfish/ shellfish/ slightly sealettuce adhered adhered 30 months slime slime slime slime slime/ slime/slightly slightly slightly slightly shellfish/ shellfish/ adheredadhered adhered adhered sea lettuce sea lettuce adhered adhered

[Testing Method]

(a) Paint Property:

The paint properties were measured in the same manner as in Example(1A), etc.

The coating applicability and the antifouling characteristics weretested in the following manner.

(b) Coating Applicability:

A soft steel plate of the size 70 mm×150 mm×1 mm thickness was bonded tothe center of a tin plate of the size 1000 mm×1000 mm×1 mm thickness,and airless spray coating was carried out while holding the tin plateupright. Whether or not the spraying device was clogged was inspected,and the limit film thickness over which film sagging occurred wasmeasured after drying of the coating film.

(c) Antifouling Test:

An epoxy undercoat paint was applied in a thickness of 200 μm over apolyvinyl chloride plate of the size 100 mm×300 mm×5 mm thickness. Eachof the antifouling paint compositions was applied by a brush over theepoxy coating film so that the dried antifouling film thickness became150 μm. After the drying for 3 days, the coated plates were immersedstill in the Bay of Miyazima for a period of 30 months. After thecompletion of the immersion, the antifouling properties were evaluatedby visual observation.

(d) Evaluation of Paint Stability and Coating Applicability:

With respect to each of the antifouling paint compositions, thecondition of paint (stability) and coating applicability after stockingat 50° C. for 3 months following the preparation thereof were tested.

Condition of Paint (Stability):

Each of the antifouling paint compositions specified in Table 2 wasplaced in a can, sealed, and allowed to stand still in a 50° C.thermostat for 3 months. The can was opened, and the paint compositionwas agitated well, followed by inspection with the use of a finenessgauge. Results are also given in the above Tables 2 and 3.

(e) Antifouling Test:

The antifouling test was performed with respect to the antifouling paintcompositions having been stocked at 50° C. for 3 months after thepreparation thereof.

Results are given in Table 4.

TABLE 4 Example 1 Example 2 Example 3 Example 4 Comp. Ex. 1 Comp. Ex. 2antifouling property  6 months normal normal normal normal slime slimeslightly adhered adhered much 12 months normal normal normal normalslime slime/ adhered shellfish much slightly adhered 18 months normalnormal normal normal slime/ slime/ shellfish shellfish slightly adheredadhered much 24 months normal normal normal normal slime/ slime/shellfish shellfish/ adhered sea lettuce much adhered 30 months slimeslime slime slime slime/ slime/ slightly slightly slightly slightlyshellfish/ shellfish/ adhered adhered adhered adhered sea lettuce sealettuce adhered adhered

Example 5

50 parts by weight of dimethylpolysiloxane containing 5 mol % ofdiphenylsiloxy units (-Ph₂SiO— wherein Ph: phenyl) per molecule andhaving both molecular chain (molecular) terminals thereof blocked byhydroxyl groups, the 25° C. viscosity of the dimethylpolysiloxane being20,000 cSt; 10 parts by weight of hydrophilic silica of 200 m²/g in BETspecific surface area; and 10 parts by weight of hydrophobic silicahaving its surface treated with hexamethyldisilazane, the BET specificsurface area of the hydrophobic silica being 130 m²/g, were agitated andmixed together at 150° C. for 2 hr. Thereafter, the mixture was dilutedwith 50 parts by weight of dimethylpolysiloxane containing 5 mol % ofdiphenylsiloxy units per molecule and having both molecular terminalsthereof blocked by hydroxyl groups, the 25° C. viscosity of thedimethylpolysiloxane being 20,000 cSt. Further, the mixture was loadedwith 10 parts by weight of methyltributanoximesilane, 0.1 part by weightof dibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed. The resultantcomposition was further loaded with 40 parts by weight of xylene,thereby obtaining a curable silicone solution of 20 mPa·s viscosity.This solution was applied by means of a coating roll machine onto analuminum wall surface, thereby obtaining a 400 micron thick coatingfilm. The composition was cured at 23° C. in 55% RH for 7 days. As aresult, there was obtained a highly transparent coating cured productwith a glossy surface, which exhibited such excellent rubber propertiesas 60 in durometer type A hardness and 4.0 MPa in tensile strength.

Comparative Example 3

50 parts by weight of dimethylpolysiloxane containing 5 mol % ofdiphenylsiloxy units per molecule and having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 20,000 cSt; and 20 parts by weight ofhydrophilic silica of 200 m²/g in BET specific surface area wereagitated and mixed together at 150° C. for 2 hr. Thereafter, the mixturewas diluted with 50 parts by weight of dimethylpolysiloxane containing 5mol % of diphenylsiloxy units per molecule and having both molecularchain terminals thereof blocked by hydroxyl groups, the 25° C. viscosityof the dimethylpolysiloxane being 20,000 cSt. Further, the mixture wasloaded with 10 parts by weight of methyltributanoximesilane, 0.1 part byweight of dibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed.

The resultant composition was further loaded with 40 parts by weight ofxylene, thereby obtaining a curable silicone solution of 13 mPa·sviscosity. This solution was applied by means of a coating roll machineonto an aluminum wall surface. The maximum coating film thicknessobtainable was 100 microns. Attempts to obtain greater coating filmthickness resulted in sagging.

Example 6

50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 20,000 cSt; 5 parts by weight ofhydrophilic silica of 200 m²/g in BET specific surface area; and 10parts by weight of hydrophobic silica having its surface treated withhexamethyldisilazane, the BET specific surface area of the hydrophobicsilica being 130 m²/g, were agitated and mixed together at 150° C. for 2hr. Thereafter, the mixture was diluted with 50 parts by weight ofdimethylpolysiloxane having both molecular chain terminals thereofblocked by hydroxyl groups, the 25° C. viscosity of thedimethylpolysiloxane being 20,000 cSt. Further, the mixture was loadedwith 10 parts by weight of methyltributanoximesilane, 0.1 part by weightof dibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed. parts by weight ofmethyl ethyl ketone was added to the mixture to thereby regulate theviscosity thereof. Thus, a curable silicone composition of 60 mPa·sviscosity was obtained. An electronic base plate was coated with thiscomposition by means of a dispenser, and the composition was cured at23° C. in 55% RH for 7 days. As a result, a glossy silicone film withvery good appearance was formed on the base plate. This film exhibitedsuch excellent rubber properties as 50 in durometer type A hardness and3.5 MPa in tensile strength.

Comparative Example 4

50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 20,000 cSt, was mixed with 15 parts byweight of hydrophobic silica having its surface treated withdimethyldichlorosilane, the BET specific surface area of the hydrophobicsilica being 130 m²/g, at room temperature.

Thereafter, the mixture was diluted with 50 parts by weight ofdimethylpolysiloxane having both molecular chain terminals thereofblocked by hydroxyl groups, the 25° C. viscosity of thedimethylpolysiloxane being 20,000 cSt. Further, the mixture was loadedwith 10 parts by weight of methyltributanoximesilane, 0.1 part by weightof dibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed. 20 parts by weightof methyl ethyl ketone was added to the mixture to thereby regulate theviscosity thereof. Thus, a curable silicone composition of 80 mPa·sviscosity was obtained.

An electronic base plate was coated with this composition by means of adispenser. The deliverability through a nozzle was poor. The compositionwas cured at 23° C. in 55% RH for 7 days. As a result, a silicone filmwith milky dull surface was formed on the base plate.

Example 7

50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 5,000 cSt; 5 parts by weight ofhydrophilic silica of 200 m²/g in BET specific surface area; and 5 partsby weight of hydrophobic silica having its surface treated withhexamethyldisilazane, the BET specific surface area of the hydrophobicsilica being 130 m²/g, were agitated and mixed together at 150° C. for 2hr. Thereafter, the mixture was diluted with 50 parts by weight ofdimethylpolysiloxane having both molecular chain terminals thereofblocked by hydroxyl groups, the 25° C. viscosity of thedimethylpolysiloxane being 5000 cSt. Further, the mixture was loadedwith 2.0 parts by weight of zinc carbonate, 10 parts by weight ofvinyltributanoximesilane and 1.5 parts by weight ofaminopropyltrimethoxysilane and also loaded with platinum catalyst insuch an amount that the platinum atom concentration was 300 ppm, andmixed. Thus, a curable silicone composition of 10 mPa·s viscosity wasobtained. Glass fiber was dip coated with this composition, and thecomposition was cured at 23° C. in 55% RH for 7 days. As a result, therewas obtained an excellent fire retardant coat film of about 1 mm nearlyuniform thickness.

Comparative Example 5

10 parts by weight of hydrophilic silica of 200 m²/g in BET specificsurface area was added to 50 parts by weight of dimethylpolysiloxanehaving both molecular chain terminals thereof blocked by hydroxylgroups, the 25° C. viscosity of the dimethylpolysiloxane being 5,000cSt, and agitated and mixed together at 150° C. for 2 hr. Thereafter,the mixture was diluted with 50 parts by weight of dimethylpolysiloxanehaving both molecular chain terminals thereof blocked by hydroxylgroups, the 25° C. viscosity of the dimethylpolysiloxane being 5000 cSt.Further, the mixture was loaded with 2.0 parts by weight of zinccarbonate, 10 parts by weight of vinyltributanoximesilane and 1.5 partsby weight of aminopropyltrimethoxysilane and also loaded with platinumcatalyst in such an amount that the platinum atom concentration was 300ppm, and mixed. Thus, a curable silicone composition of 4 Pa·s viscositywas obtained. Glass fiber was dip coated with this composition, and thecomposition was cured at 23° C. in 55% RH for 7 days. Sagging anddropping occurred during the curing step, so that a fire retardant curedproduct of uniform thickness was not obtained.

Example 8

100 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 1,000,000 cSt; 30 parts by weight ofhydrophilic silica of 200 m²/g in BET specific surface area; 15 parts byweight of hydrophobic silica having its surface treated withdimethyldichlorosilane, the BET specific surface area of the hydrophobicsilica being 130 m²/g; and 10 parts by weight of dimethylpolysiloxanehaving both molecular chain terminals thereof blocked by hydroxylgroups, the average polymerization degree of the dimethylpolysiloxanebeing 13, were agitated and mixed together at 150° C. for 2 hr. Theresultant composition was loaded with 10 parts by weight ofvinyltributanoximesilane, 1.5 parts by weight ofaminopropyltrimethoxysilane and 65 parts by weight of xylene. Thus,there was obtained a composition of high thixotropy exhibiting aviscosity, as measured by BL rotary viscometer, of 60 Pa·s upon 4rotations and 4 Pa·s upon 20 rotations. This composition was cured at23° C. in 55% RH for 7 days. As a result, there was obtained a highlytransparent coating cured product with a glossy surface, which exhibitedsuch excellent rubber properties as 65 in durometer type A hardness and8.0 MPa in tensile strength.

Comparative Example 6

100 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 1,000,000 cSt; 45 parts by weight ofhydrophilic silica of 200 m²/g in BET specific surface area; and 10parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the average polymerizationdegree of the dimethylpolysiloxane being 13, were agitated and mixedtogether at 150° C. for 2 hr. The resultant composition was loaded with10 parts by weight of vinyltributanoximesilane, 1.5 parts by weight ofaminopropyltrimethoxysilane and 65 parts by weight of xylene. Theobtained composition had rather low thixotropy exhibiting a viscosity,as measured by BL !rotary viscometer, of 12 Pa·s upon 4 rotations and 9Pa·s upon 20 rotations.

Comparative Example 7

100 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 1,000,000 cSt; 45 parts by weight ofhydrophobic silica having its surface treated withdimethyldichlorosilane, the BET specific surface area of the hydrophobicsilica being 200 m²/g; and 10 parts by weight of dimethylpolysiloxanehaving both molecular chain terminals thereof blocked by hydroxylgroups, the average polymerization degree of the dimethylpolysiloxanebeing 13, were agitated and mixed together at room temperature for 2 hr.The resultant composition was loaded with 10 parts by weight ofvinyltributanoximesilane, 1.5 parts by weight ofaminopropyltrimethoxysilane and 65 parts by weight of xylene. Theobtained composition had a high thixotropy exhibiting a viscosity, asmeasured by BM rotary viscometer, of 850 Pa·s upon 4 rotations and 180Pa·s upon 20 rotations, but the viscosity thereof was extremely high.

Example 9

50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by trimethoxysiloxy groups (—O—Si—(OCH₃)₃),the 25° C. viscosity of the dimethylpolysiloxane being 20,000 cSt; 5parts by weight of hydrophilic silica (fumed silica) of 200 m²/g in BETspecific surface area; and 5 parts by weight of hydrophobic fumed silicahaving its surface treated with hexamethyldisilazane, the BET specificsurface area of the hydrophobic fumed silica being 130 m²/g, wereagitated and mixed together at 150° C. for 2 hr. Thereafter, the mixturewas diluted with 50 parts by weight of dimethylpolysiloxane having bothmolecular chain terminals thereof blocked by trimethoxysiloxy groups,the 25° C. viscosity of the dimethylpolysiloxane being 20,000 cSt.Further, the mixture was loaded with 5 parts by weight ofmethyltrimethoxysilane, 0.1 part by weight of dibutyltin dioctoate and1.0 part by weight of aminopropyltrimethoxysilane, and deaerated andmixed. 20 parts by weight of methyl ethyl ketone was added to themixture to thereby regulate the viscosity thereof. Thus, curablesilicone composition 1L (hardening composition 1L) of 200 mPa·sviscosity was obtained. This composition was cured at 23° C. in 55% RHfor 7 days. As a result, a glossy silicone film with very goodappearance was formed on a base plate. This cured product exhibited suchexcellent rubber properties as 40 in durometer type A hardness and 2.7MPa in tensile strength (as measured in accordance with JapaneseIndustrial Standard 6249).

Comparative Example 8

50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by trimethoxysiloxy groups, the 25° C.viscosity of the dimethylpolysiloxane being 20,000 cSt, was agitated andmixed with 10 parts by weight of hydrophobic fumed silica having a BETspecific surface area of 200 m²/g at room temperature for 2 hr.Thereafter, the mixture was diluted with 50 parts by weight ofdimethylpolysiloxane having both molecular chain terminals thereofblocked by trimethoxysiloxy groups, the 25° C. viscosity of thedimethylpolysiloxane being 20,000 cSt. Further, the mixture was loadedwith 5 parts by weight of methyltrimethoxysilane, 0.1 part by weight ofdibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed. 20 parts by weightof methyl ethyl ketone was added to the mixture to thereby regulate theviscosity thereof. Thus, a curable silicone composition (1M) of 480mPa·s viscosity was obtained. An electronic base plate was coated withthis composition (1M) by means of a dispenser. The deliverabilitythrough a nozzle was poorer than that of the composition of Example 9.The composition was cured at 23° C. in 55% RH for 7 days. As a result, asilicone film with milky dull surface was formed on the base plate. Thiscured product exhibited a durometer type A hardness of 35 and a tensilestrength of 2.0 MPa (as measured in accordance with Japanese IndustrialStandard 6249).

It is apparent from the results of Examples 5 to 9 and ComparativeExamples 3 to 8 that the curable compositions of the present inventionhave low viscosity and high thixotropy and are excellent in not onlycoating applicability but also coating film strength, surface smoothnessand other properties.

Examples 10 to 13 and Comparative Examples 9 to 12

Antifouling paint compositions were prepared in the same manner as inExample 1, except that, in place of the organopolysiloxane composition(1A) of Example 1, curable silicone composition 1L of Example 9 wasemployed in Examples 10 to 13 and curable silicone composition 1M ofComparative Example 8 was employed in Comparative Examples 9 to 12 andexcept that silicone oil and xylene were used in amounts specified inTable 5. The properties of the obtained antifouling paint compositionswere evaluated in the same manner as in Example 1.

Results are given in Tables 5 to 8.

Table 5, like Table 2, lists the properties and coating applicability ofcurable compositions formulated into paints. Table 6, like Table 3,lists the antifouling properties exhibited after conversion into paints.Table 7 lists the properties of paints having been stored for a givenperiod of time. Table 8, like Table 4, lists the antifouling propertiesexhibited by paints after storage.

TABLE 5 Comp. Comp. Comp. Example 10 Example 11 Example 12 Example 13Comp. Ex. 9 Ex. 10 Ex. 11 Ex. 12 organopolysiloxane (paint) cmpsn. type1L 1L 1L 1L 1M 1M 1M 1M amt. 100 100 100 100 100 100 100 100 siliconeoil SH550 *7 20 (21) TSF431 *8 60 (64) 70 (75) 40 (43) KF50 *9 80 (85)60 (64) 30 (32) 30 (32) 60 (64) silicone oil of Synthetic Ex. 1 30 (32)40 (43) KF-6016 *10 10 (11) xylene 5 5 5 5 5 5 5 5 properties of paintviscosity (Pa · s/25° C.) 110 100 90 100 190 180 150 230 specificgravity (20° C.) 0.99 0.99 0.99 0.99 0.99 0.99 0.99 0.99 applicabilitysprayability good good good good clogged clogged clogged clogged sagging(limit film thickness μm) 180 160 150 170 130 120 110 140 *7: producedby Dow Corning Toray Silicone Co., Ltd. *8: produced by Toshiba SiliconeCo., Ltd. *9: produced by Shin-Etsu Chemical Co., Ltd. *10: produced byShin-Etsu Chemical Co., Ltd. Note: parenthesized amount of silicone oilsindicates the addition amount (pts. wt.) per 100 parts by weight oforganopolysiloxane (A).

TABLE 6 Example 10 Example 11 Example 12 Example 13 Comp. Ex. 9 Comp.Ex. 10 Comp. Ex. 11 Comp. Ex. 12 antifouling property  6 months normalnormal normal normal normal slime slime slime slightly slightly slightlyadhered adhered adhered 12 months normal normal normal normal slimeslime slime slime slightly slightly slightly slightly adhered adheredadhered adhered 18 months normal normal normal normal slime/ slimeslime/ slime/ shellfish slightly shellfish shellfish slightly adheredadhered adhered adhered much much 24 months normal normal normal normalslime/ slime/ slime/ slime/ shellfish shellfish/ shellfish/ shellfish/adhered sea lettuce sea lettuce sea lettuce much adhered adhered adhered30 months slime slime slime slime slime/ slime/ slime/ slime/ slightlyslightly slightly slightly shellfish/ shellfish/ shellfish/ shellfish/adhered adhered adhered adhered sea lettuce sea lettuce sea lettuce sealettuce adhered adhered adhered adhered

TABLE 7 Comp. Comp. Example 10 Example 11 Example 12 Example 13 Comp.Ex. 9 Comp. Ex. 10 Ex. 11 Ex. 12 organopolysiloxane compsn. type 1L 1L1L 1L 1M 1M 1M 1M amt. 100 100 100 100 100 100 100 100 silicone oilSH550 *7 20 (21) TSF431 *8 60 (64) 70 (75) 40 (43) KF50 *9 80 (85) 60(64) 30 (32) 30 (32) 60 (64) silicone oil of Synthetic Ex. 1 30 (32) 40(43) KF-6016 *10 10 xylene 5 5 5 5 5 5 5 5 after 3 months at 50° C.condition of paint (stability) normal normal normal normal gelatinizedgelatinized gelatinized gelatinized sprayability good good good goodclogged clogged clogged clogged sagging (limit film thickness 180 160150 170 110 110 100 120 μm) *7: produced by Dow Corning Toray SiliconeCo., Ltd. *8: produced by Toshiba Silicone Co., Ltd. *9: produced byShin-Etsu Chemical Co., Ltd. *10: produced by Shin-Etsu Chemical Co.,Ltd. Note: parenthesized amount of silicone oils indicates the additionamount (pts. wt.) per 100 parts by weight of organopolysiloxane (A).

TABLE 8 Example 10 Example 11 Example 12 Example 13 Comp. Ex. 9 Comp.Ex. 10 Comp. Ex. 11 Comp. Ex. 12 antifouling property  6 months normalnormal normal normal slime slime/ slime slime slightly slightly adheredadhered adhered adhered much much 12 months normal normal normal normalslime/ slime/ slime/ slime/ shellfish shellfish shellfish shellfishslightly slightly slightly slightly adhered adhered adhered adhered 18months normal normal normal normal slime/ slime/ slime/ slime/ shellfishshellfish shellfish shellfish adhered adhered adhered adhered much muchmuch much 24 months normal normal normal normal slime/ slime/ slime/slime/ shellfish shellfish/ shellfish/ shellfish/ adhered sea lettucesea lettuce sea lettuce much adhered adhered adhered 30 months slimeslime slime slime slime/ slime/ slime/ slime/ slightly slightly slightlyslightly shellfish/ shellfish/ shellfish/ shellfish/ adhered adheredadhered adhered sea lettuce sea lettuce sea lettuce sea lettuce adheredadhered adhered adhered

Preparation of organopolysiloxane paint compositions (2A) to (2F)indicated in Table 9.

Curable organopolysiloxane paint compositions of the formulations (2A)to (2F) specified in Table 9 were prepared in the same manner as theorganopolysiloxane paint composition (1A) specified in Table 1.

The properties and physical characteristics of coating film thereof aregiven in Table 9. The testing method and *1 to *6 of Table 9 are thesame as those described with respect to the organopolysiloxane paintcompositions (1A) to (1F) of Table 1.

TABLE 9 Organopolysiloxane paint composition Example Comp. Ex. 2A 2B 2C2D 2E 2F organopolysiloxane *1 50 25 25 0 0 0 thermally treatedhydrophobic fumed silica mixture *2 60 90 90 120 (hydrophobic fumedsilica *5) (10) (15) (15) (20) (organopolysiloxane *6) (50) (75) (75)(100)  room temp. treated hydrophobic fumed silica mixture *3 120(hydrophobic fumed silica *5)  (20) (organopolysiloxane *6) (100)thermally treated hydrophilic silica mixture *4) 120 (hydrophilic silica*5)  (20) (organopolysiloxane *6) (100) (total organopolysiloxane (A)component in compsn.) (100)  (100)  (100)  (100)  (100) (100)methyltri(methylethylketoxime) silane 10 10 10 10 methyltriacetoxysilane7 7 dibutyltin dilaurate 0.1 0.1 0.1 0.1 0.1 0.1 xylene 20 20 20 20 2020 properties viscosity (Pa · s/25° C.) 0.7 0.8 0.8 0.6 0.8 0.5 specificgravity (20° C.) 0.99 0.99 0.99 0.99 0.89 0.98 physical characteristicof film hardness (JIS-K) 45 47 47 49 39 45 tensile strength (MPa) 3.53.6 3.8 3.8 2.9 3.5 elongation (%) 230 210 210 200 170 190 *1, 2, 3, 4,5: produced by Shin-Etsu Chemical Co., Ltd. *1: organopolysiloxane(weight) added at the time of composition preparation. *2, 3, 4: numericvalue indicates the addition amount (weight) ofsilica/organopolysiloxane treatment product. *5: silica (weight)contained in silica/organopolysiloxane treatment product. *6:organopolysiloxane (weight) contained in silica/organopolysiloxanetreatment product.

Examples 14 to 17, Comparative Examples 13 and 14

Silicone oil and xylene were mixed, in proportions indicated in Table10, with 100 parts by weight of each of the organopolysiloxane paintcompositions (2A) to (2F) specified in Table 9, and agitated untilbecoming homogeneous, thereby obtaining antifouling paint compositions.

The properties and coating applicability of each of the antifoulingpaint compositions were measured in the above manner.

Results are given in Table 10.

The antifouling test of each of the antifouling paint compositionsimmediately after preparation was carried out in the above manner.

Results are given in Table 11.

The *7, *8, *9 and *10 and testing method of Table 10 are the same asaforementioned. The parenthesized amount of various silicone oils isparts by weight added per 100 parts by weight of organopolysiloxane (A),as aforementioned.

With respect to each of the antifouling paint compositions, thecondition of paint (stability) and coating applicability after stockingat 50° C. for 3 months after the preparation thereof were tested in theaforementioned manner.

Results are also given in Table 10.

Furthermore, with respect to each of the antifouling paint compositionshaving been stocked at 50° C. for 3 months after the preparationthereof, the aforementioned antifouling test was carried out.

Results are given in Table 12.

TABLE 10 Example 14 Example 15 Example 16 Example 17 Comp. Ex. 13 Comp.Ex. 14 organopolysiloxane compsn. type 2A 2B 2C 2D 2E 2F amt. 100 100100 100 100 100 silicone oil SH550 *7 50 (53) TSF431 *8 60 (64) 40 (43)KF50-100 *9 20 (21) 80 (85) 60 (64) 30 (32) 30 (32) organopolysiloxaneof Synthetic 30 (32) 40 (43) Ex. 1 (silicone oil (D)) KF-6016 *10 xylene10 10 10 10 10 10 properties of paint viscosity (Pa · s/25° C.) 0.4 0.50.4 0.5 0.5 0.2 specific gravity (20° C.) 0.99 0.99 0.99 0.99 0.99 0.99applicability sprayability good good good good good good sagging (limitfilm thickness μm) 180 180 170 180 160 130 after 3 months at 50° C.condition of paint (stability) normal normal normal normal gelatinizedgelatined sprayability good good good good clogged clogged sagging(limit film thickness μm) 180 180 170 180 140 110 *7: produced by DowCorning Toray Silicone Co., Ltd. *8: produced by Toshiba Silicone Co.,Ltd. *9: produced by Shin-Etsu Chemical Co., Ltd. *10: produced byShin-Etsu Chemical Co., Ltd. Note: parenthesized amount of silicone oilsindicates the addition amount (pts. wt.) per 100 parts by weight ofsolid contents produced from organopolysiloxane compsn.

TABLE 11 Example 14 Example 15 Example 16 Example 17 Comp. Ex. 13 Comp.Ex. 14 antifouling property  6 months normal normal normal normal normalnormal 12 months normal normal normal normal normal normal 18 monthsnormal normal normal normal normal slime slightly adhered 24 monthsnormal normal normal normal slime/ slime/ shellfish shellfish/ slightlysea lettuce adhered adhered 30 months slime slime slime slime slime/slime/ slightly slightly slightly slightly shellfish/ shellfish/ adheredadhered adhered adhered sea lettuce sea lettuce adhered adhered

TABLE 12 Example 14 Example 15 Example 16 Example 17 Comp. Ex. 13 Comp.Ex. 14 antifouling property  6 months normal normal normal normal slimeslime slightly adhered adhered much 12 months normal normal normalnormal slime slime/ adhered shellfish much adhered much 18 months normalnormal normal normal slime/ slime/ shellfish shellfish slightly adheredadhered much 24 months normal normal normal normal slime/ slime/shellfish shellfish/ adhered lettuce much adhered 30 months slime slimeslime slime slime/ slime/ slightly slightly slightly slightly shellfish/shellfish/ adhered adhered adhered adhered lettuce lettuce adheredadhered

Example 18

50 parts by weight of dimethylpolysiloxane containing 5 mol % ofdiphenylsiloxy units (-Ph₂SiO— wherein Ph: phenyl) per molecule andhaving both molecular chain (molecular) terminals thereof blocked byhydroxyl groups, the 25° C. viscosity of the dimethylpolysiloxane being20,000 cSt; and 20 parts by weight of hydrophobic fumed silica havingits surface treated with hexamethyldisilazane, the BET specific surfacearea of the hydrophobic fumed silica being 130 m²/g, were agitated andmixed together at 150° C. for 2 hr. Thereafter, the mixture was dilutedwith 50 parts by weight of dimethylpolysiloxane containing 5 mol % ofdiphenylsiloxy units per molecule and having both molecular terminalsthereof blocked by hydroxyl groups, the 25° C. viscosity of thedimethylpolysiloxane being 20,000 cSt. Further, the mixture was loadedwith 10 parts by weight of methyltributanoximesilane, 0.1 part by weightof dibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed. The resultantcomposition was further loaded with 40 parts by weight of xylene,thereby obtaining a curable silicone solution of 28 mPa·s. This solutionwas applied by means of a coating roll machine onto an aluminum wallsurface, thereby obtaining a 400 micron thick coating film. Thecomposition was cured at 23° C. in 55% RH for 7 days. As a result, therewas obtained a highly transparent coating cured product with a glossysurface, which exhibited such excellent rubber properties as 58 indurometer type A hardness and 4.5 MPa in tensile strength.

Comparative Example 15

50 parts by weight of dimethylpolysiloxane containing 5 mol % ofdiphenylsiloxy units per molecule and having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 20,000 cSt; and 20 parts by weight offumed silica of 200 m²/g in BET specific surface area were agitated andmixed together at 150° C. for 2 hr. Thereafter, the mixture was dilutedwith 50 parts by weight of dimethylpolysiloxane containing 5 mol % ofdiphenylsiloxy units per molecule and having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 20,000 cSt. Further, the mixture wasloaded with 10 parts by weight of methyltributanoximesilane, 0.1 part byweight of dibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed. The resultantcomposition was further loaded with 40 parts by weight of xylene,thereby obtaining a curable silicone solution of 13 mPa·s. This solutionwas applied by means of a coating roll machine onto an aluminum wallsurface. The maximum coating film thickness obtainable was 100 microns.Attempts to obtain greater coating film thickness resulted in sagging.

Example 19

50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 20,000 cSt; and 10 parts by weight ofhydrophobic fumed silica having its surface treated withhexamethyldisilazane, the BET specific surface area of the hydrophobicfumed silica being 130 m²/g, were agitated and mixed together at 150° C.for 2 hr. Thereafter, the mixture was diluted with 50 parts by weight ofdimethylpolysiloxane having both molecular chain terminals thereofblocked by hydroxyl groups, the 25° C. viscosity of thedimethylpolysiloxane being 20,000 cSt. Further, the mixture was loadedwith 10 parts by weight of methyltributanoximesilane, 0.1 part by weightof dibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed. 20 parts by weightof methyl ethyl ketone was added to the mixture to thereby regulate theviscosity thereof. Thus, a curable silicone composition of 45 mPa·sviscosity was obtained. An electronic base plate was coated with thiscomposition by means of a dispenser, and the composition was cured at23° C. in 55% RH for 7 days. As a result, a silicone film with very goodappearance was formed on the base plate. This film exhibited suchexcellent rubber properties as 35 in durometer type A hardness and 2.7MPa in tensile strength.

Comparative Example 16

50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 20,000 cSt, was mixed with 15 parts byweight of hydrophobic fumed silica having its surface treated withdimethyldichlorosilane, the BET specific surface area of the hydrophobicfumed silica being 130 m²/g, at room temperature.

Thereafter, the mixture was diluted with 50 parts by weight ofdimethylpolysiloxane having both molecular chain terminals thereofblocked by hydroxyl groups, the 25° C. viscosity of thedimethylpolysiloxane being 20,000 cSt. Further, the mixture was loadedwith 10 parts by weight of methyltributanoximesilane, 0.1 part by weightof dibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed. 20 parts by weightof methyl ethyl ketone was added to the mixture to thereby regulate theviscosity thereof. Thus, a curable silicone composition of 80 mPa·sviscosity was obtained.

An electronic base plate was coated with this composition by means of adispenser. The deliverability through a nozzle was poor. The compositionwas cured at 23° C. in 55% RH for 7 days. As a result, a silicone filmwith milky dull surface was formed on the base plate.

Example 20

50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 5,000 cSt; and 10 parts by weight ofhydrophobic fumed silica having its surface treated withhexamethyldisilazane, the BET specific surface area of the hydrophobicfumed silica being 130 m²/g, were agitated and mixed together at 150° C.for 2 hr. Thereafter, the mixture was diluted with 50 parts by weight ofdimethylpolysiloxane having both molecular chain terminals thereofblocked by hydroxyl groups, the 25° C. viscosity of thedimethylpolysiloxane being 5000 cSt. Further, the mixture was loadedwith 2.0 parts by weight of zinc carbonate, 10 parts by weight ofvinyltributanoximesilane and 1.5 parts by weight ofaminopropyltrimethoxysilane and also loaded with platinum catalyst insuch an amount that the platinum atom concentration was 300 ppm, andmixed. Thus, a curable silicone composition of 15 mPa·s viscosity wasobtained. Glass fiber was dip coated with this composition, and thecomposition was cured at 23° C. in 55% RH for 7 days. As a result, therewas obtained an excellent fire retardant coat film of about 1 mm nearlyuniform thickness.

Comparative Example 17

10 parts by weight of fumed silica of 200 m²/g in BET specific surfacearea was added to 50 parts by weight of dimethylpolysiloxane having bothmolecular chain terminals thereof blocked by hydroxyl groups, the 25° C.viscosity of the dimethylpolysiloxane being 5,000 cSt, and agitated andmixed together at 150° C. for 2 hr. Thereafter, the mixture was dilutedwith 50 parts by weight of dimethylpolysiloxane having both molecularchain terminals thereof blocked by hydroxyl groups, the 25° C. viscosityof the dimethylpolysiloxane being 5000 cSt. Further, the mixture wasloaded with 2.0 parts by weight of zinc carbonate, 10 parts by weight ofvinyltributanoximesilane and 1.5 parts by weight ofaminopropyltrimethoxysilane and also loaded with platinum catalyst insuch an amount that the platinum atom concentration was 300 ppm, andmixed. Thus, a curable silicone composition of 4 Pa·s viscosity wasobtained. Glass fiber was dip coated with this composition, and thecomposition was cured at 23° C. in 55% RH for 7 days. Sagging anddropping occurred during the curing step, so that a fire retardant curedproduct of uniform thickness was not obtained.

Example 21

100 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 1,000,000 cSt; 45 parts by weight ofhydrophobic fumed silica having its surface treated withdimethyldichlorosilane, the BET specific surface area of the hydrophobicfumed silica being 130 m²/g; and 10 parts by weight ofdimethylpolysiloxane having both molecular chain terminals thereofblocked by hydroxyl groups, the average polymerization degree of thedimethylpolysiloxane being 13, were agitated and mixed together at 150°C. for 2 hr. The resultant composition was loaded with 10 parts byweight of vinyltributanoximesilane, 1.5 parts by weight ofaminopropyltrimethoxysilane and 65 parts by weight of xylene. Thus,there was obtained a composition of high thixotropy exhibiting aviscosity, as measured by BL rotary viscometer, of 100 Pa·s upon 4rotations and 15 Pa's upon 20 rotations. This composition was cured at23° C. in 55% RH for 7 days. As a result, there was obtained a highlytransparent coating cured product, which exhibited such excellent rubberproperties as 65 in durometer type A hardness and 6.5 MPa in tensilestrength.

Comparative Example 18

100 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 1,000,000 cSt; 45 parts by weight offumed silica of 200 m²/g in BET specific surface area; and 10 parts byweight of dimethylpolysiloxane having both molecular chain terminalsthereof blocked by hydroxyl groups, the average polymerization degree ofthe dimethylpolysiloxane being 13, were agitated and mixed together at150° C. for 2 hr. The resultant composition was loaded with 10 parts byweight of vinyltributanoximesilane, 1.5 parts by weight ofaminopropyltrimethoxysilane and 65 parts by weight of xylene. Theobtained composition had rather low thixotropy exhibiting a viscosity,as measured by BL rotary viscometer, of 12 Pa·s upon 4 rotations and 9Pa·s upon 20 rotations.

Comparative Example 19

100 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by hydroxyl groups, the 25° C. viscosity ofthe dimethylpolysiloxane being 1,000,000 cSt; 45 parts by weight ofhydrophobic fumed silica having its surface treated withdimethyldichlorosilane, the BET specific surface area of the hydrophobicfumed silica being 200 m²/g; and 10 parts by weight ofdimethylpolysiloxane having both molecular chain terminals thereofblocked by hydroxyl groups, the average polymerization degree of thedimethylpolysiloxane being 13, were agitated and mixed together at roomtemperature for 2 hr. The resultant composition was loaded with 10 partsby weight of vinyltributanoximesilane, 1.5 parts by weight ofaminopropyltrimethoxysilane and 65 parts by weight of xylene. Theobtained composition had a high thixotropy exhibiting a viscosity, asmeasured by BM rotary viscometer, of 850 Pa·s upon 4 rotations and 180Pa·s upon 20 rotations, but the viscosity thereof was extremely high.

Example 22

50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by trimethoxysiloxy groups (—O—Si—(OCH₃)₃),the 25° C. viscosity of the dimethylpolysiloxane being 20,000 cSt; and10 parts by weight of hydrophobic fumed silica having its surfacetreated with hexamethyldisilazane, the BET specific surface area of thehydrophobic fumed silica being 130 m²/g, were agitated and mixedtogether at 150° C. for 2 hr. Thereafter, the mixture was diluted with50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by trimethoxysiloxy groups, the 25° C.viscosity of the dimethylpolysiloxane being 20,000 cSt. Further, themixture was loaded with 5 parts by weight of methyltrimethoxysilane, 0.1part by weight of dibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed. 20 parts by weightof methyl ethyl ketone was added to the mixture to thereby regulate theviscosity thereof. Thus, curable silicone composition 2L (curablecomposition 2L) of 400 mPa·s viscosity was obtained. This compositionwas cured at 23° C. in 55% RH for 7 days. As a result, a silicone filmwith very good appearance was formed on a base plate. This cured productexhibited such excellent rubber properties as 40 in durometer type Ahardness and 2.0 MPa in tensile strength (as measured in accordance withJapanese Industrial Standard 6249).

Comparative Example 20

50 parts by weight of dimethylpolysiloxane having both molecular chainterminals thereof blocked by trimethoxysiloxy groups, the 25° C.viscosity of the dimethylpolysiloxane being 20,000 cSt, was agitated andmixed with 10 parts by weight of hydrophobic fumed silica having a BETspecific surface area of 200 m²/g at room temperature for 2 hr.Thereafter, the mixture was diluted with 50 parts by weight ofdimethylpolysiloxane having both molecular chain terminals thereofblocked by trimethoxysiloxy groups, the 25° C. viscosity of thedimethylpolysiloxane being 20,000 cSt. Further, the mixture was loadedwith 5 parts by weight of methyltrimethoxysilane, 0.1 part by weight ofdibutyltin dioctoate and 1.0 part by weight ofaminopropyltrimethoxysilane, and deaerated and mixed. 20 parts by weightof methyl ethyl ketone was added to the mixture to thereby regulate theviscosity thereof. Thus, a curable silicone composition (2M) of 480mPa·s viscosity was obtained. An electronic base plate was coated withthis composition (2M) by means of a dispenser. The deliverabilitythrough a nozzle was poorer than that of the composition of Example 9.The composition was cured at 23° C. in 55% RH for 7 days. As a result, asilicone film with milky dull surface was formed on the base plate. Thiscured product exhibited a durometer type A hardness of 35 and a tensilestrength of 2.0 MPa (as measured in accordance with Japanese IndustrialStandard 6249). It is apparent from the results of Examples 18 to 22 andComparative Examples 15 to 20 that the curable compositions of thepresent invention have low viscosity and high thixotropy and areexcellent in not only coating applicability but also coating filmstrength, surface smoothness and other properties.

Examples 23 to 26 and Comparative Examples 21 to 24

Antifouling paint compositions were prepared in the same manner as inExample 14, except that, in place of the organopolysiloxane composition2A of Example 14, curable silicone composition 2L of Example 22 wasemployed in Examples 23 to 26 and curable silicone composition 2M ofComparative Example 20 was employed in Comparative Examples 21 to 24 andexcept that silicone oil and xylene were used in amounts specified inTable 13. The properties of the obtained antifouling paint compositionswere evaluated in the same manner as in Example 14.

Results are given in Tables 13 to 16.

Table 13, like Table 10, lists the properties and coating applicabilityof curable compositions formulated into paints. Table 14, like Table 11,lists the antifouling properties exhibited after conversion into paints.Table 15, like Table 10, lists the properties of paints having beenstored for a given period of time. Table 16, like Table 12, lists theantifouling properties exhibited by paints after storage.

TABLE 13 Example Example Example Example 23 24 25 26 Comp. Ex. 21 Comp.Ex. 22 Comp. Ex. 23 Comp. Ex. 24 organopolysiloxane compsn. type 2L 2L2L 2L 2M 2M 2M 2M amt. 100 100 100 100 100 100 100 100 silicone oilSH550 *7 50 (53) 20 (21) TSF431 *8 60 (64) 40 (43) 70 (75) KF50-100 *920 (21) 80 (85) 60 (64) 30 (32) 30 (32) 60 (64) silicone oil ofSynthetic Ex. 1 30 (32) 40 (43) KF-6016 *10 10 (11) xylene 5 5 5 5 5 5 55 properties of paint viscosity (Pa · s/25° C.) 100 110 100 90 190 180150 150 specific gravity (20° C.) 0.99 0.99 0.99 0.99 0.99 0.99 0.990.99 applicability sprayability good good good good clogged cloggedclogged clogged sagging (limit film thickness μm) 170 180 160 150 130120 110 110 *7: produced by Dow Corning Toray Silicone Co., Ltd. *8:produced by Toshiba Silicone Co., Ltd. *9: produced by Shin-EtsuChemical Co., Ltd. *10: produced by Shin-Etsu Chemical Co., Ltd. Note:parenthesized amount of silicone oils indicates the addition amount(pts. wt.) per 100 parts by weight of solid contents produced fromorganopolysiloxane compsn.

TABLE 14 Example 23 Example 24 Example 25 Example 26 Comp. Ex. 21 Comp.Ex. 22 Comp. Ex. 23 Comp. Ex. 24 anitfouling property  6 months normalnormal normal normal normal slime slime slime slightly slightly slightlyadhered adhered adhered 12 months normal normal normal normal slimeslime slime slime slightly slightly slightly slightly adhered adheredadhered adhered 18 months normal normal normal normal slime/ slimeslime/ slime/ shellfish slightly shellfish shellfish slightly adheredadhered adhered adhered much much 24 months normal normal normal normalslime/ slime/ slime/ slime/ shellfish shellfish/ shellfish/ shellfish/adhered sea lettuce sea lettuce sea lettuce much adhered adhered adhered30 months slime slime slime slime slime/ slime/ slime/ slime/ slightlyslightly slightly slightly shellfish/ shellfish/ shellfish/ shellfish/adhered adhered adhered adhered sea lettuce sea lettuce sea lettuce sealettuce adhered adhered adhered adhered

TABLE 15 Example Example Example Example 23 24 25 26 Comp. Ex. 21 Comp.Ex. 22 Comp. Ex. 23 Comp. Ex. 24 organopolysiloxane compsn. type 2L 2L2L 2L 2M 2M 2M 2M amt. 100 100 100 100 100 100 100 100 silicone oilSH550 *7 50 (53) 20 (21) TSF431 *8 60(64) 40 (43) 70(75) KF50-100 *9 20(21) 80 (85) 60 (64) 30 (32) 30 (32) 60 (64) silicone oil of SyntheticEx. 1 30 (32) 40 (43) KF-6016 *10 10 (11) xylene 5 5 5 5 5 5 5 5 after 3months at 50° C. condition of paint (stability) normal normal normalnormal gelatinized gelatinized gelatinized gelatinized sprayability goodgood good good clogged clogged clogged clogged sagging (limit filmthickness μm) 170 180 160 150 110 110 100 100 *7: produced by DowCorning Toray Silicone Co., Ltd. *8: produced by Toshiba Silicone Co.,Ltd. *9: produced by Shin-Etsu Chemical Co., Ltd. *10: produced byShin-Etsu Chemical Co., Ltd. Note: parenthesized amount of silicone oilsindicates the addition amount (pts. wt.) per 100 parts by weight ofsolid contents produced from organopolysiloxane compsn.

TABLE 16 Example 23 Example 24 Example 25 Example 26 Comp. Ex. 21 Comp.Ex. 22 Comp. Ex. 23 Comp. Ex. 24 antifouling property  6 months normalnormal normal normal slime slightly slime slightly slime adhered slimeadhered adhered adhered much much 12 months normal normal normal normalslime/shellfish slime/shellfish slime/shellfish slime/shellfish slightlyslightly adhered much adhered much adhered adhered 18 months normalnormal normal normal slime/shellfish slime/shellfish slime/shellfishslime/shellfish adhered much adhered much adhered much adhered much 24months normal normal normal normal slime/shellfish slime/shellfish/slime/shellfish/ slime/shellfish/ adhered much sea lettuce sea lettucesea lettuce adhered adhered adhered 30 months slime slightly slimeslightly slime slightly slime slightly slime/shellfish/ slime/shellfish/slime/shellfish/ slime/shellfish/ adhered adhered adhered adhered sealettuce sea lettuce sea lettuce sea lettuce adhered adhered adheredadhered

What is claimed is:
 1. A curable composition comprising: (A) anorganopolysiloxane having functional groups capable of condensationreaction at both molecular terminals thereof, and (B) a hydrophobicsilica and a hydrophilic silica, wherein at least the hydrophilic silicaamong the hydrophobic silica and hydrophilic silica is thermally treatedtogether with the organopolysiloxane (A).
 2. The curable composition asclaimed in claim 1, wherein the organopolysiloxane (A) is represented bythe formula:

wherein W represents a hydroxyl group or a hydrolyzable group; each ofR¹ and R independently represents an unsubstituted or substitutedmonovalent hydrocarbon group having 1 to 12 carbon atoms, provided thatthe hydrocarbon groups R¹ as well as the hydrocarbon groups R may beidentical with or different from each other; n is an integer of 5 orgreater; and a is 0, 1 or
 2. 3. The curable composition as claimed inclaim 2, wherein, in the formula (α), W represents a hydroxyl group anda is 2, wherein the curable composition further comprises in addition tothe components (A) and (B): (C) an organosilane represented by theformula: R¹ _(b)SiX_(4−b)  (I)  wherein R¹ represents an unsubstitutedor substituted monovalent hydrocarbon group having 1 to 8 carbon atoms;X represents a hydrolyzable group; and b is 0 or 1, or a partialhydrolyzate of the organosilane.
 4. The curable composition as claimedin claim 1, wherein the hydrophilic silica is thermally treated at 100°C. or higher together with the organopolysiloxane (A).
 5. The curablecomposition as claimed in claim 1, wherein the hydrophobic silica andhydrophilic silica (B) is contained in an amount of 1 to 100 parts byweight per 100 parts by-weight of the organopolysiloxane (A).
 6. Thecurable composition as claimed in claim 3, wherein the organosilane orpartial hydrolyzate thereof (C) is contained in an amount of 1 to 20parts by weight per 100 parts by weight of the organopolysiloxane (A).7. The curable composition as claimed in claim 1, wherein thehydrophobic silica (a) and the hydrophilic silica (b) are contained at aweight ratio ((a)/(b)) of 1/99 to 99/1.
 8. The curable composition asclaimed in claim 1, further comprising a silicone oil (D) in a totalamount of 0.1 to 200 parts by weight per 100 parts by weight of theorganopolysiloxane (A).
 9. The curable composition as claimed in claim1, further comprising any one or more of a catalyst, an antifoulingagent or a colorant.
 10. A process for producing the curable compositionas claimed in claim 1, comprising heating the organopolysiloxane (A) andat least the hydrophilic silica among the hydrophobic silica andhydrophilic silica (B) at 100° C. or higher.
 11. A coating compositioncomprising the curable composition claimed in claim
 1. 12. The coatingcomposition as claimed in claim 11, which is used as a paint.
 13. Thecoating composition as claimed in claim 12, wherein the paint is anantifouling paint.
 14. A cured product of the curable compositionclaimed in claim
 1. 15. An antifouling coating film comprising thecurable composition claimed in claim
 1. 16. An antifouling coated basematerial comprising a base material brought into contact with sea wateror fresh water, having its surface covered with a coating film obtainedby curing the curable composition claimed in claim
 1. 17. Theantifouling base material as claimed in claim 16, wherein the basematerial is used in any of underwater structures, ship shell plates,fishing nets and fishing gears.
 18. A method of rendering a basematerial antifouling, comprising coating or impregnating a surface of abase material with an antifouling paint comprising the curablecomposition claimed in claim 1, and subsequently curing the coatingcomposition to thereby form an antifouling coating film.
 19. The methodas set forth in claim 18, wherein the base material is used in any ofunderwater structures, ship shell plates, fishing nets and fishinggears.
 20. An antifouling paint comprising the curable composition asclaimed in claim
 1. 21. A method of coating an underwater structurecomprising coating the underwater structure with an antifouling paintaccording to claim
 20. 22. A method of coating a ship shell platecomprising coating the ship shell plate with an antifouling paintaccording to claim
 20. 23. A method of coating a fishing net comprisingcoating the fishing net with an antifouling paint according to claim 20.24. A method of coating fishing gear comprising coating the fishing gearwith an antifouling paint according to claim 20.